JP2003299965A - Photocatalyst material and production method of the same - Google Patents
Photocatalyst material and production method of the sameInfo
- Publication number
- JP2003299965A JP2003299965A JP2002107043A JP2002107043A JP2003299965A JP 2003299965 A JP2003299965 A JP 2003299965A JP 2002107043 A JP2002107043 A JP 2002107043A JP 2002107043 A JP2002107043 A JP 2002107043A JP 2003299965 A JP2003299965 A JP 2003299965A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst material
- photocatalyst
- noble metal
- crystal
- photocatalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 267
- 239000000463 material Substances 0.000 title claims abstract description 216
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 85
- 230000001699 photocatalysis Effects 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 79
- 239000010419 fine particle Substances 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 21
- 239000002923 metal particle Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims description 147
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 87
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 87
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 69
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 23
- 238000005240 physical vapour deposition Methods 0.000 claims description 17
- 239000010970 precious metal Substances 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 11
- 238000004544 sputter deposition Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000004687 hexahydrates Chemical class 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- QFJIELFEXWAVLU-UHFFFAOYSA-H tetrachloroplatinum(2+) dichloride Chemical compound Cl[Pt](Cl)(Cl)(Cl)(Cl)Cl QFJIELFEXWAVLU-UHFFFAOYSA-H 0.000 claims description 5
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 8
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 238000001465 metallisation Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 41
- 239000000758 substrate Substances 0.000 description 27
- 239000002585 base Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 18
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 150000002902 organometallic compounds Chemical class 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000009467 reduction Effects 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 241000554155 Andes Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001877 deodorizing effect Effects 0.000 description 3
- 238000001312 dry etching Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 102000003729 Neprilysin Human genes 0.000 description 1
- 108090000028 Neprilysin Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 108010007127 Pulmonary Surfactant-Associated Protein D Proteins 0.000 description 1
- 102100027845 Pulmonary surfactant-associated protein D Human genes 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940063821 oxygen 21 % Drugs 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は光触媒材料とその製
造方法に関し、特に、酸化物光触媒において、特異な結
晶形状と表面構造を有し、高活性の光触媒機能を得るこ
とができる酸化物光触媒材料とその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst material and a method for producing the same, and more particularly to an oxide photocatalyst material having a unique crystal shape and surface structure and capable of obtaining a highly active photocatalytic function. And its manufacturing method.
【０００２】[0002]
【従来の技術】酸化チタンに代表される酸化物光触媒
は、そのバンドギャップ以上のエネルギーを持つ波長の
光を照射すると、光励起により光触媒機能を発現するこ
とは従来から知られている。光触媒機能の発現機構は、
光励起により伝導帯に電子を生じ、価電子帯に正孔を生
じることに起因する。電子の強い還元力、正孔の強い酸
化力により、光触媒に接触してくる有機物や窒素酸化物
を水や炭酸ガスなどに分解するものであり、防汚、防
臭、抗菌機能等を有している。2. Description of the Related Art It is conventionally known that an oxide photocatalyst typified by titanium oxide exhibits a photocatalytic function by photoexcitation when irradiated with light having a wavelength having an energy larger than its band gap. The expression mechanism of the photocatalytic function is
This is because photoexcitation produces electrons in the conduction band and holes in the valence band. Due to the strong reducing power of electrons and the strong oxidizing power of holes, it decomposes organic substances and nitrogen oxides that come into contact with the photocatalyst into water and carbon dioxide, and has antifouling, deodorizing, and antibacterial functions. There is.
【０００３】このような酸化物光触媒の防汚、防臭、抗
菌機能を利用した環境浄化方法、装置が現在注目されて
いる。つまり、昨今の水質汚染、大気汚染等の環境汚染
問題に起因するものである。このような状況において、
環境浄化方法の高性能化および高効率化を図るために
は、酸化物光触媒自体の光触媒機能の高活性化が求めら
れる。At present, an environmental purification method and apparatus utilizing the antifouling, deodorizing, and antibacterial functions of such oxide photocatalysts are drawing attention. That is, it is caused by recent environmental pollution problems such as water pollution and air pollution. In this situation,
In order to improve the performance and efficiency of the environmental purification method, it is required to highly activate the photocatalytic function of the oxide photocatalyst itself.
【０００４】酸化物光触媒材料は通常粉末状で用いられ
ていたため、取り扱いが非常に難しく、環境浄化装置に
組み込むのは困難であった。粉末状の酸化物光触媒を固
定化するために、粉末状の酸化物光触媒を有機バインダ
ーと混合して基材上に塗布し、それを常温下または加熱
して固定させる方法がある。しかし、この方法は有機物
が酸化物光触媒表面の一部または大部分を覆ってしまう
ため、光触媒機能は粉末そのものに比べ、著しく不活性
化するという欠点があった。さらに光触媒機能によって
有機物である有機バインダーが分解されてしまうため、
被膜強度が劣化し、粉末が次第に脱落してしまう、とい
う耐久性に係るもう一つの大きな問題がある。光触媒機
能は、光触媒が表面に露出して初めて機能を発揮するも
のである。無機バインダーで粉末状の酸化物光触媒を固
定化した場合、粉末の脱落という欠点は克服されたが、
酸化物光触媒の一部をバインダ−が覆うため、光触媒機
能発現のために有効な表面の面積が減少し、光触媒機能
が著しく低下してしまうという問題は改善されることは
なかった。Since the oxide photocatalyst material is usually used in the form of powder, it is very difficult to handle, and it has been difficult to incorporate it into an environmental purification device. In order to fix the powdery oxide photocatalyst, there is a method in which the powdery oxide photocatalyst is mixed with an organic binder and applied onto a base material, and the mixture is fixed at room temperature or by heating. However, this method has a drawback that the photocatalytic function is significantly inactivated as compared with the powder itself because the organic material covers a part or most of the surface of the oxide photocatalyst. Furthermore, since the organic binder, which is an organic substance, is decomposed by the photocatalytic function,
There is another major problem related to durability, in which the film strength deteriorates and the powder gradually falls off. The photocatalytic function exhibits its function only when the photocatalyst is exposed on the surface. When the powdered oxide photocatalyst was fixed with an inorganic binder, the disadvantage of powder falling off was overcome,
Since the binder covers a part of the oxide photocatalyst, the effective surface area for expressing the photocatalytic function is reduced, and the problem that the photocatalytic function is significantly deteriorated has not been solved.
【０００５】上記の粉末状酸化物光触媒の問題点を解決
するべく、特開平８−２６６９１０、特開平９−１９２
４９８等に開示される真空蒸着法、特開平８−３０９２
０４、特開平１１−１２７２０等に開示されるスパッタ
リング法、特開平７−１００３７８、特開平１０−１８
０１１８等に開示されるゾル−ゲル法など、これまで数
多くの酸化物光触媒の作製技術が提案されている。これ
らの先行技術により上述の粉末状酸化物の問題点の解決
が試みられ、光触媒機能の改善が図られているが、その
高活性化という点からは、満足なものが得られてはいな
かった。In order to solve the above problems of the powdery oxide photocatalyst, JP-A-8-266910 and JP-A-9-192 have been proposed.
498 and the like, the vacuum deposition method disclosed in JP-A-8-3092.
04, JP-A-11-12720, etc., JP-A-7-100378, JP-A-10-18.
Many techniques for producing an oxide photocatalyst have been proposed so far, such as the sol-gel method disclosed in 0118 and the like. Although these prior arts have attempted to solve the above-mentioned problems of the powdery oxide and have attempted to improve the photocatalytic function, satisfactory results have not been obtained from the viewpoint of high activation. .
【０００６】上述のように光触媒機能は、光が照射され
る光触媒体表面で起こるものである。このため光触媒機
能の高活性化を目的に光触媒体の表面状態を制御する技
術、あるいは光触媒体表層部の結晶を制御する技術が従
来から提案されている。光触媒体の表面状態を制御する
技術として特開平９―５７９１２号公報、特開平１０−
３６１４４号公報、特開平１０―５７８１７号公報およ
び特開平１０―２３１１４６号公報が開示されている。
これら先行技術に開示される基本構成は、ガラス基板の
表面に直接あるいはアルカリ遮断用の下地膜を介して光
触媒としての酸化チタン層が形成され、この酸化チタン
層の表面に酸化ケイ素を形成したものである。As described above, the photocatalytic function occurs on the surface of the photocatalyst which is irradiated with light. Therefore, a technique for controlling the surface state of the photocatalyst body or a technique for controlling the crystal of the surface layer of the photocatalyst body has been proposed in order to highly activate the photocatalyst function. As a technique for controlling the surface condition of the photocatalyst body, JP-A-9-57912 and JP-A-10-
JP-A-36144, JP-A-10-57817 and JP-A-10-231146 are disclosed.
The basic configuration disclosed in these prior arts is one in which a titanium oxide layer as a photocatalyst is formed directly on the surface of a glass substrate or through an alkali blocking base film, and silicon oxide is formed on the surface of this titanium oxide layer. Is.
【０００７】上記の各先行技術は、酸化ケイ素膜を多孔
質に形成したり、酸化チタン膜やガラス基板に微細加工
を施すことにより表面上に凹凸を設けることで、光触媒
機能を高める工夫をしている。Each of the above-mentioned prior arts is devised to enhance the photocatalytic function by forming a silicon oxide film in a porous manner or by finely processing a titanium oxide film or a glass substrate to form irregularities on the surface. ing.
【０００８】すなわち、表面に微細な凹凸を形成するこ
とで光触媒が露出する表面の面積が増大することによっ
て光触媒機能が向上するというものであるが、必ずしも
顕著な向上は達成できなかった。また基板の加工、膜の
加工、下地層の挿入などコスト面でも問題があった。That is, the photocatalytic function is improved by increasing the area of the surface where the photocatalyst is exposed by forming fine irregularities on the surface, but it was not always possible to achieve a remarkable improvement. Further, there are problems in terms of cost such as substrate processing, film processing, and underlayer insertion.
【０００９】光触媒体表層部を構成する結晶を制御する
技術として、特開平２０００―２８８４０３が開示され
ている。その基本構成はアナターゼ型酸化チタン結晶で
あり、その表層部に存在する酸化チタンの結晶粒のうち
３０％以上の結晶粒の形状が楕円形又は半楕円形であ
り、これにより高活性の光触媒機能が得られるというも
のである。これは、結晶粒を楕円形又は半楕円形にする
ことで光触媒体の露出する表面積が増加し、光触媒機能
が向上するというものであるが、必ずしも顕著な向上は
見られなかった。Japanese Unexamined Patent Publication No. 2000-288403 has been disclosed as a technique for controlling crystals constituting the surface layer of the photocatalyst. Its basic structure is anatase-type titanium oxide crystal, and 30% or more of the titanium oxide crystal grains present in the surface layer have an elliptical or semi-elliptical shape, which results in a highly active photocatalytic function. Is obtained. This means that the exposed surface area of the photocatalyst increases and the photocatalytic function is improved by making the crystal grains elliptical or semi-elliptical, but the remarkable improvement was not necessarily found.
【００１０】[0010]
【発明が解決しようとする課題】上述した従来技術にお
いては、各種作製方法により形成された酸化物光触媒、
また光触媒体表面状態の制御および光触媒体の表面層部
を構成する結晶を制御することで形成した酸化物光触媒
は、一定の光触媒機能の改善が図られてはいるが、さら
に高活性の光触媒機能を有する酸化物光触媒が求められ
ている。In the above-mentioned prior art, the oxide photocatalyst formed by various manufacturing methods,
The oxide photocatalyst formed by controlling the surface state of the photocatalyst and controlling the crystals that make up the surface layer of the photocatalyst has a certain level of improvement in the photocatalytic function, but a more highly active photocatalytic function. There is a need for oxide photocatalysts having
【００１１】上述の問題点に対して本願発明者らは、結
晶形状の制御による酸化物光触媒の高活性化に主眼を置
き、化学的蒸着法（以下、「ＣＶＤ法」という。）、物
理的蒸着法（以下、「ＰＶＤ法」という。）等の各種製
法、および、有機金属化合物または無機金属化合物を用
いたゾル−ゲル法による酸化物光触媒の作製について鋭
意検討した。その結果、ＣＶＤ法またはＰＶＤ法などの
各種製法により作製した結晶核を有機金属化合物もしく
は無機金属化合物から成るゾル溶液中に入れ、または該
結晶核にゾル溶液を塗布し、固化、熱処理して、酸化チ
タン結晶を該結晶核より成長させる方法を見出した。そ
して該結晶核より成長させた酸化チタン結晶の結晶形状
が柱状結晶を成し、かつその結晶内部が中空構造を成
す、柱状中空構造の結晶（以下、「柱状中空結晶」とも
いう。）とすることで、高活性の光触媒機能が得られる
ことを突き止めた。そしてこの発見に基づいて新規なる
光触媒材料を発明、開発し、非公知の特許出願（特願２
００１−０５８９１７、特願２００１−０５８９１８）
に開示した。With respect to the above-mentioned problems, the inventors of the present application focus on the high activation of the oxide photocatalyst by controlling the crystal shape, and the chemical vapor deposition method (hereinafter, referred to as “CVD method”) and physical method. Various studies such as a vapor deposition method (hereinafter referred to as “PVD method”) and preparation of an oxide photocatalyst by a sol-gel method using an organic metal compound or an inorganic metal compound were earnestly studied. As a result, the crystal nuclei produced by various manufacturing methods such as the CVD method or the PVD method are put in a sol solution composed of an organometallic compound or an inorganic metal compound, or the sol solution is applied to the crystal nuclei, solidified, and heat-treated, A method of growing a titanium oxide crystal from the crystal nucleus was found. The crystal shape of the titanium oxide crystal grown from the crystal nuclei forms a columnar crystal, and the inside of the crystal forms a hollow structure to form a columnar hollow structure crystal (hereinafter, also referred to as “columnar hollow crystal”). Therefore, it was found that a highly active photocatalytic function can be obtained. Based on this discovery, a new photocatalyst material was invented and developed, and an unknown patent application (Japanese Patent Application 2
(001-058917, Japanese Patent Application No. 2001-058918)
Disclosed in.
【００１２】図６は、係る既開発の柱状中空構造を有す
る酸化チタン結晶による光触媒材料の外観を示す模式図
である。図において既開発の光触媒材料６０は、光触媒
材料担持体５１の表面に固定されるための基部５２と、
該基部５２から伸長する、中空の柱状構造である柱状中
空構造をとる光触媒結晶体５３と、から主として構成さ
れており、たとえば、ガラス、金属、セラミックスまた
は網目状構造を有する繊維等の各種の基板などの光触媒
材料担持体５１上に担持される、結晶核などの基部５２
から柱状中空構造の酸化チタン結晶５３が成長している
構造を有する（特願２００１−０５８９１７、特願２０
０１−０５８９１８）。ここで、柱状の結晶とは、角
柱、円柱状等の結晶形状、または枝分かれした樹枝状の
結晶形状、柱状結晶が複数本成長する途中で融合した形
状などを全て含んだ総称である。FIG. 6 is a schematic view showing the appearance of a photocatalyst material formed of titanium oxide crystals having such a developed hollow columnar structure. In the figure, a photocatalyst material 60 already developed has a base 52 for being fixed to the surface of the photocatalyst material carrier 51,
And a photocatalyst crystal body 53 having a columnar hollow structure, which is a hollow columnar structure extending from the base 52, and various substrates such as glass, metal, ceramics or fibers having a network structure. A base 52 such as a crystal nucleus, which is carried on a photocatalyst material carrier 51 such as
Has a structure in which a columnar hollow titanium oxide crystal 53 is grown (Japanese Patent Application Nos. 2001-058917 and 20).
01-058918). Here, the columnar crystal is a general term including all crystal shapes such as a prism and a column, a branched dendritic crystal shape, and a shape in which a plurality of columnar crystals are fused during the growth.
【００１３】得られた光触媒材料は、担持体である基材
に固着しているため、紛末状光触媒のような飛散の問題
を解決することができた。また、濃度２０ｐｐｍのアセ
トアルデヒドガスを１ｐｐｍ以下にまで減少させるのに
要する時間は、粉末状光触媒と比較して約５０％とな
り、アセトアルデヒドガス分解速度が約２倍になるな
ど、光触媒として極めて高活性であり、大気浄化システ
ムなどその実用化にも非常に有効なものが得られた。Since the obtained photocatalyst material is fixed to the base material which is a carrier, the problem of scattering such as powder photocatalyst could be solved. Further, the time required to reduce the acetaldehyde gas having a concentration of 20 ppm to 1 ppm or less is about 50% as compared with the powdery photocatalyst, and the decomposition rate of acetaldehyde gas is approximately doubled. Therefore, we have obtained a very effective system such as an air purification system.
【００１４】しかし、光触媒技術をさらに高度化し、そ
の応用分野を一層拡大、発展させるためには、さらなる
光触媒機能の高活性化が求められる。すなわち本発明の
解決しようとする課題は、本願発明者らが先に提案し
た、高い分解性能を有する柱状中空結晶の光触媒材料を
凌ぐ光触媒機能を備えた光触媒材料およびその製造方法
を提供することである。However, in order to further enhance the photocatalyst technology and further expand and develop its application field, further activation of the photocatalyst function is required. That is, the problem to be solved by the present invention is to provide a photocatalyst material having a photocatalytic function that surpasses the photocatalytic material of a columnar hollow crystal having a high decomposition performance, which was previously proposed by the present inventors, and a method for producing the same. is there.
【００１５】[0015]
【課題を解決するための手段】本願発明者らはこのよう
な状況に鑑み、柱状中空酸化チタン結晶において光触媒
機能のさらなる高活性化を目的とし、柱状中空結晶の構
造制御による光触媒機能の高活性化について鋭意検討し
た。その結果、柱状中空結晶の表面に白金等の貴金属微
粒子を担持させることによりさらに高活性の光触媒機能
が得られることを見出し、本発明を完成するに至った。
すなわち、本願で特許請求される発明は以下のとおりで
ある。In view of such a situation, the inventors of the present application have aimed to further enhance the photocatalytic function of the columnar hollow titanium oxide crystal, and have a high photocatalytic function by controlling the structure of the columnar hollow crystal. I made a thorough study on the conversion. As a result, they have found that a highly active photocatalytic function can be obtained by supporting fine metal particles such as platinum on the surface of the columnar hollow crystal, and have completed the present invention.
That is, the invention claimed in the present application is as follows.
【００１６】（１）光触媒材料担持体の表面に固定され
るための基部、または光触媒材料担持体の表面に固定さ
れている基部と、該基部から伸長する柱状の光触媒結晶
体と、からなる光触媒材料であって、該光触媒材料の表
面には貴金属微粒子が担持されていることを特徴とす
る、光触媒材料。(1) A photocatalyst comprising a base portion fixed to the surface of the photocatalyst material carrier, or a base portion fixed to the surface of the photocatalyst material carrier, and a columnar photocatalyst crystal body extending from the base portion. A photocatalyst material, characterized in that noble metal fine particles are carried on the surface of the photocatalyst material.
【００１７】（２）光触媒材料担持体の表面に固定され
るための基部、または光触媒材料担持体の表面に固定さ
れている基部と、該基部から伸長する中空の柱状構造を
とる光触媒結晶体と、からなる光触媒材料であって、該
光触媒材料の表面には貴金属微粒子が担持されているこ
とを特徴とする、光触媒材料。(2) A base for fixing on the surface of the photocatalyst material carrier, or a base for fixing on the surface of the photocatalyst material carrier, and a photocatalyst crystal having a hollow columnar structure extending from the base. A photocatalyst material comprising: a photocatalyst material, characterized in that noble metal fine particles are carried on the surface of the photocatalyst material.
【００１８】（３）前記光触媒結晶体内部に光触媒粒子
からなる構造が存在していることを特徴とする、（２）
の光触媒材料。(3) A structure comprising photocatalyst particles is present inside the photocatalyst crystal, (2)
Photocatalytic material.
【００１９】（４）（１）ないし（３）のいずれかの光
触媒材料であって、触媒担持面積が７５ｍｍ×７５ｍｍ
の光触媒材料担持体上に担持された担持量約０．１ｇの
光触媒を用いてなる該光触媒材料を用いてアセトアルデ
ヒドガスを分解させた場合に、容積２０リットルのガラ
ス製容器中のアセトアルデヒドガス濃度を２０ｐｐｍか
ら１ｐｐｍ以下にするための所要時間が５分以上１０分
間以下であることを特徴とする、光触媒材料。(4) The photocatalytic material according to any one of (1) to (3), which has a catalyst supporting area of 75 mm × 75 mm.
When the acetaldehyde gas is decomposed by using the photocatalyst material having a carrying amount of about 0.1 g carried on the photocatalyst material carrier, the acetaldehyde gas concentration in a glass container having a volume of 20 liters is A photocatalyst material, characterized in that the time required for reducing from 20 ppm to 1 ppm is 5 minutes or more and 10 minutes or less.
【００２０】（５）前記光触媒が酸化チタンであり、前
記基部が結晶核であり、前記貴金属は白金であることを
特徴とする、（１）ないし（４）のいずれかの光触媒材
料。(5) The photocatalyst material according to any one of (1) to (4), wherein the photocatalyst is titanium oxide, the base is a crystal nucleus, and the noble metal is platinum.
【００２１】（６）光触媒材料担持体と、該光触媒材料
担持体上に担持された（１）ないし（５）のいずれかの
光触媒材料と、からなる光触媒体。(6) A photocatalyst body comprising a photocatalyst material carrier and the photocatalyst material of any one of (1) to (5) carried on the photocatalyst material carrier.
【００２２】（７）貴金属が表面に担持されていない光
触媒材料を得る原光触媒材料作製工程と、得られた原光
触媒材料の表面に貴金属微粒子を担持するための貴金属
担持工程とからなる光触媒材料製造方法であって、該貴
金属担持工程は、光触媒材料を貴金属化合物溶液に浸漬
して貴金属粒子を光触媒材料表面に吸着、担持する吸着
工程と、貴金属が吸着、担持された光触媒材料を乾燥し
次いで熱処理する乾燥熱処理工程と、を含むことを特徴
とする、光触媒材料製造方法。(7) Photocatalyst material production comprising a raw photocatalyst material preparation step for obtaining a photocatalyst material in which noble metal is not supported on the surface, and a noble metal support step for supporting noble metal fine particles on the surface of the obtained raw photocatalyst material In the method, the noble metal supporting step comprises an adsorption step of immersing the photocatalyst material in a solution of a noble metal compound to adsorb and support the noble metal particles on the surface of the photocatalyst material; And a heat treatment step for drying the photocatalyst material.
【００２３】（８）前記乾燥熱処理工程の後に、前記光
触媒材料表面に担持された酸化状態の貴金属微粒子を還
元するための還元工程を設けることを特徴とする、
（７）の光触媒材料製造方法。(8) After the dry heat treatment step, a reducing step for reducing the oxidized noble metal fine particles carried on the surface of the photocatalytic material is provided.
(7) The method for producing a photocatalytic material.
【００２４】（９）前記貴金属化合物がヘキサクロロ白
金（VI）酸六水和物等の白金を含む化合物であることを
特徴とする、（７）または（８）の光触媒材料製造方
法。(9) The method for producing a photocatalyst material according to (7) or (8), wherein the noble metal compound is a compound containing platinum such as hexachloroplatinum (VI) acid hexahydrate.
【００２５】（１０）貴金属が表面に担持されていない
光触媒材料を得る原光触媒材料作製工程と、得られた原
光触媒材料の表面に貴金属を担持するため貴金属担持工
程とからなる光触媒材料製造方法であって、該貴金属担
持工程は、スパッタリング法、真空蒸着法、またはその
他の物理的蒸着法により原光触媒材料の表面に貴金属微
粒子を担持させる工程であることを特徴とする、光触媒
材料製造方法。(10) A method for producing a photocatalyst material comprising a raw photocatalyst material producing step for obtaining a photocatalyst material in which noble metal is not supported on the surface and a precious metal supporting step for carrying a noble metal on the surface of the obtained raw photocatalyst material. The photocatalytic material manufacturing method is characterized in that the noble metal supporting step is a step of supporting noble metal fine particles on the surface of the raw photocatalytic material by a sputtering method, a vacuum deposition method, or another physical vapor deposition method.
【００２６】本発明は、本願発明者らが既に開発し、上
述した非公知の特許出願において開示した柱状中空構造
を有する酸化チタン光触媒結晶の表面に貴金属微粒子を
担持させることにより、さらに高活性の光触媒材料を得
るというものである。The present invention has a higher activity by supporting the noble metal fine particles on the surface of the titanium oxide photocatalyst crystal having the columnar hollow structure which has been already developed by the present inventors and disclosed in the above-mentioned unknown patent application. That is to obtain a photocatalytic material.
【００２７】前記酸化チタン光触媒結晶は、有機金属化
合物または無機金属化合物のゾル溶液中に結晶核を入
れ、または結晶核にゾル溶液を塗布し、固化、熱処理し
て該結晶核より成長させることを特徴とする。柱状中空
構造を有する酸化チタン結晶自体も既に非常に高活性で
あるが、これに貴金属微粒子を担持させることでさらに
その活性を向上させることができ、アセトアルデヒド等
の有機有害物質の分解効率を約２倍にまで向上させるこ
とができる。The titanium oxide photocatalyst crystal may be grown from the crystal nucleus by putting the crystal nucleus in a sol solution of an organometallic compound or an inorganic metal compound, or by applying the sol solution to the crystal nucleus, solidifying and heat treating. Characterize. The titanium oxide crystals themselves having a columnar hollow structure are already very active, but the activity can be further improved by supporting them with noble metal particles, and the decomposition efficiency of organic harmful substances such as acetaldehyde is about 2 Can be doubled.
【００２８】すなわち本発明に係る代表的な酸化物光触
媒材料は、結晶核から成長させた柱状中空構造を有する
酸化チタン結晶であって、その表面に白金等の貴金属の
微粒子を担持させたものであり、その担持は、貴金属担
持前の光触媒材料を貴金属化合物の溶液に浸漬して該光
触媒材料の表面に貴金属微粒子を吸着させ、乾燥及び熱
処理によってこれを固化することによって行う。また
は、スパッタ法等のＰＶＤ法によって行う。That is, a typical oxide photocatalyst material according to the present invention is a titanium oxide crystal having a columnar hollow structure grown from crystal nuclei, on the surface of which fine particles of precious metal such as platinum are carried. The supporting is carried out by immersing the photocatalyst material before supporting the noble metal in a solution of the noble metal compound to adsorb the noble metal fine particles on the surface of the photocatalyst material, and drying and heat treatment to solidify the noble metal fine particles. Alternatively, a PVD method such as a sputtering method is used.
【００２９】本発明において、光触媒結晶の形状が柱状
とは、角柱状、円柱状、棒状、その他柱状の立体構造を
とるものをすべて含み、また該柱状結晶は鉛直方向に真
っ直ぐに伸びるもの、傾斜状に伸びるもの、湾曲しなが
ら伸びるもの、枝状に分岐して伸びるもの、柱状結晶が
複数本成長し途中で融合したもの等を含む。In the present invention, the columnar shape of the photocatalyst crystal includes all prismatic, columnar, rod-shaped, and other columnar three-dimensional structures, and the columnar crystals extend straight in the vertical direction and have a slant. It includes those extending in a shape, those extending while curving, those branching and branching, those in which a plurality of columnar crystals grow and are fused in the middle, and the like.
【００３０】結晶核はスパッタリング法、真空蒸着法等
のＰＶＤ法、またはＣＶＤ法で作製した結晶核のみなら
ず、その種類は単結晶、多結晶体、その他を広く用いる
ことができる。また結晶核としては、通常の化学反応に
見られる様に明らかに核と認められないようなもの、た
とえば基板上の傷等を核の代替物とすることも可能であ
る。柱状結晶構造は、結晶核上に一つ以上の柱状結晶を
成長させ、結晶核とその上に成長させる柱状結晶が同一
方位に成長し、典型的なものでは柱状結晶の内部は中空
構造を有していることを特徴とする。柱状結晶構造を有
する光触媒は、従来の他の結晶形状を有するものに比べ
て分解対象物との接触効率が良く、分解性能が飛躍的に
向上する。As the crystal nuclei, not only crystal nuclei prepared by a PVD method such as a sputtering method or a vacuum deposition method or a CVD method, but also a single crystal, a polycrystal, or the like can be widely used as the kind. Further, as crystal nuclei, it is possible to use, as a substitute for the nuclei, those which are clearly not recognized as nuclei as seen in ordinary chemical reactions, for example, scratches on the substrate. In the columnar crystal structure, one or more columnar crystals are grown on the crystal nuclei, and the crystal nuclei and the columnar crystals grown on the crystal nuclei grow in the same direction, and typically, the columnar crystals have a hollow structure inside. It is characterized by doing. A photocatalyst having a columnar crystal structure has a better contact efficiency with an object to be decomposed than a conventional one having another crystal shape, and the decomposition performance is dramatically improved.
【００３１】なお本願発明者らは先に、本発明とは別
に、柱状中空結晶の外壁部をドライエッチングやウェッ
トエッチング等の手法を用いて一部取り除き、光触媒微
粒子からなる構造を含む中空構造となっている内部を外
部に露出させる技術により、外壁部を取り除かない柱状
中空結晶と比較して分解性能を高める方法を、非公知の
特許出願において提案した（特願２００１−３９２８０
４）。この方法と、本発明の貴金属微粒子担持の柱状中
空結晶光触媒材料の製造方法とを併用することにより、
その相乗効果によって、さらに光触媒材料の分解性能を
高めることができる。In addition to the present invention, the inventors of the present application previously removed a part of the outer wall portion of the columnar hollow crystal using a method such as dry etching or wet etching to obtain a hollow structure including a structure composed of photocatalyst fine particles. In a non-known patent application, a method of enhancing decomposition performance by a technique of exposing the inside to the outside is proposed in Japanese Patent Application No. 2001-39280.
4). By using this method in combination with the method for producing a columnar hollow crystal photocatalytic material supporting noble metal fine particles of the present invention,
The synergistic effect can further enhance the decomposition performance of the photocatalyst material.
【００３２】この場合、前記柱状中空結晶の中空内部構
造を外部に露出させる手法としては、ドライエッチング
手法、ウェットエッチング手法、機械的方法が有効であ
る。ドライエッチング手法には物理的エッチング方法と
化学的エッチング方法がある。物理的エッチング方法と
してはイオンエッチング法、プラズマエッチング法等が
あり、化学的エッチング方法としてはガスエッチング法
等がある。ウェットエッチング手法は、強無機酸、強酸
化剤、フッ化物などを基礎的な組成として含むエッチン
グ溶液を用いるものである。さらに機械的方法とは、柱
状中空結晶を研磨することによって中空内部構造を表面
に露出させる方法である。これらの方法により、柱状中
空結晶の外壁部が一部取り除かれ、中空内部構造が外部
に露出し、高活性の光触媒機能が得られる。In this case, as a method for exposing the hollow internal structure of the columnar hollow crystal to the outside, a dry etching method, a wet etching method and a mechanical method are effective. The dry etching method includes a physical etching method and a chemical etching method. The physical etching method includes an ion etching method and a plasma etching method, and the chemical etching method includes a gas etching method. The wet etching method uses an etching solution containing a strong inorganic acid, a strong oxidant, a fluoride, etc. as a basic composition. Further, the mechanical method is a method of exposing the hollow internal structure on the surface by polishing the columnar hollow crystals. By these methods, the outer wall portion of the columnar hollow crystal is partly removed, the hollow internal structure is exposed to the outside, and a highly active photocatalytic function is obtained.
【００３３】また、柱状中空の酸化チタン結晶作製工程
において、１５℃／ｍｉｎ〜１０５℃／ｍｉｎ、または
２０℃／ｍｉｎ〜１００℃／ｍｉｎの昇温速度で熱処理
することにより、結晶形成に大きく寄与する熱伝導速度
が上昇し、柱状構造の外壁部を構成する結晶の結晶密度
が低くなることによって柱状中空結晶の中空内部構造が
露出し、光触媒機能の高活性化が達成される。In the columnar hollow titanium oxide crystal production process, heat treatment is performed at a temperature rising rate of 15 ° C./min to 105 ° C./min, or 20 ° C./min to 100 ° C./min, which greatly contributes to crystal formation. The heat conduction rate is increased and the crystal density of the crystals forming the outer wall of the columnar structure is lowered, so that the hollow internal structure of the columnar hollow crystal is exposed, and the photocatalytic function is highly activated.
【００３４】[0034]
【発明の実施の形態】以下、本発明を、図面によりさら
に詳細に説明する。図１は本発明の光触媒材料の外観を
示す模式図である。図において本光触媒材料1０は、光
触媒材料担持体１の表面に固定されるための基部２と、
該基部２から伸長する柱状構造をとる光触媒結晶体３
と、該光触媒結晶体３および該基部２の表面に担持され
た貴金属微粒子５と、から主として構成されており、た
とえば、ガラス、金属、セラミックスまたは網目状構造
を有する繊維等の各種の基板などの光触媒材料担持体１
上に担持される、結晶核などの基部２から柱状構造の酸
化チタン結晶が光触媒結晶体３として成長し、該基部２
および該光触媒結晶体３の表面には白金等の貴金属微粒
子５が担持されている構造を有する。なお図は模式図で
あり、特に光触媒結晶体３等に対する貴金属微粒子５の
大きさは強調され、またその分布状態も模式的に表した
ものである。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in more detail with reference to the drawings. FIG. 1 is a schematic view showing the appearance of the photocatalytic material of the present invention. In the figure, the present photocatalyst material 10 comprises a base 2 for being fixed to the surface of the photocatalyst material carrier 1,
Photocatalytic crystal 3 having a columnar structure extending from the base 2.
And noble metal fine particles 5 carried on the surface of the photocatalyst crystal body 3 and the base portion 2, for example, various substrates such as glass, metal, ceramics or fibers having a mesh structure. Photocatalyst material carrier 1
A columnar titanium oxide crystal grows as a photocatalyst crystal body 3 from a base 2 such as a crystal nucleus supported on the base 2.
And, the photocatalyst crystal body 3 has a structure in which the noble metal fine particles 5 such as platinum are carried on the surface. The figure is a schematic diagram, and in particular, the size of the noble metal fine particles 5 with respect to the photocatalyst crystal body 3 and the like is emphasized, and the distribution state thereof is also schematically shown.
【００３５】前記光触媒結晶体３は、中空の柱状構造
（以下、「柱状中空構造」ともいう。）をとるものとす
ることができ、また該光触媒結晶体３内部には、図示し
ない光触媒粒子からなる構造６（以下、「結晶粒子」と
もいう。）が存在している構成とすることができる。The photocatalyst crystal body 3 can have a hollow columnar structure (hereinafter, also referred to as "columnar hollow structure"), and the inside of the photocatalyst crystal body 3 contains photocatalyst particles (not shown). The structure 6 (hereinafter, also referred to as “crystal particle”) is present.
【００３６】前記光触媒結晶体３には酸化チタンを用
い、また、前記基部２には、該光触媒結晶体３を成長さ
せるための結晶核を用いることができる。 結晶核はス
パッタリング法、真空蒸着法等のＰＶＤ法、またはＣＶ
Ｄ法で作製した結晶核のみならず、その種類は単結晶、
多結晶体、粉体、セラミックス、金属の熱酸化膜、陽極
酸化膜のいずれでもかまわない。また、結晶核として
は、通常の化学反応に見られる様に明らかに核と認めら
れないようなもの、たとえば基板上の傷、異物の突起等
のように、基板上にあって基板とは相違する状態を有す
る部分を核の代替物とすることも可能である。柱状結晶
構造は、結晶核上に一つ以上の柱状結晶を成長させ、結
晶核とその上に成長させる柱状結晶が同一方位に成長
し、典型的なものでは柱状結晶の内部は中空構造を有し
ていることを特徴とする。Titanium oxide can be used for the photocatalyst crystal body 3, and crystal nuclei for growing the photocatalyst crystal body 3 can be used for the base 2. Crystal nuclei are PVD methods such as sputtering method and vacuum deposition method, or CV
Not only the crystal nuclei produced by the D method, but the types are single crystals,
It may be a polycrystal, powder, ceramics, thermal oxide film of metal, or anodic oxide film. Also, as crystal nuclei, those that are not clearly recognized as nuclei as seen in normal chemical reactions, such as scratches on the substrate and protrusions of foreign matter, are on the substrate and are different from the substrate. It is also possible to use a portion having a state of being a substitute for the nucleus. In the columnar crystal structure, one or more columnar crystals are grown on the crystal nuclei, and the crystal nuclei and the columnar crystals grown on the crystal nuclei grow in the same direction, and typically, the columnar crystals have a hollow structure inside. It is characterized by doing.
【００３７】前記貴金属としては白金（以下、「Ｐｔ」
とも記載する。）を用いることができるが、本発明はこ
れに限定されず、Ｐｔに替えて、パラジウム（以下、
「Ｐｄ」とも記載する。）、金（以下、「Ａｕ」とも記
載する。）、銀（以下、「Ａｇ」とも記載する。）、イ
リジウム（以下、「Ｉｒ」とも記載する。）、ロジウム
（以下、「Ｒｈ」とも記載する。）、ルテニウム（以
下、「Ｒｕ」とも記載する。）等を用いることもでき
る。Platinum (hereinafter referred to as "Pt") is used as the noble metal.
Also described. ) Can be used, but the present invention is not limited to this, and palladium (hereinafter,
Also referred to as "Pd". ), Gold (hereinafter also referred to as “Au”), silver (hereinafter also referred to as “Ag”), iridium (hereinafter also referred to as “Ir”), rhodium (hereinafter also referred to as “Rh”). ), Ruthenium (hereinafter, also referred to as “Ru”), and the like.
【００３８】本発明の光触媒材料１０は、たとえばガラ
ス、金属、セラミックスまたは網目状構造を有する繊維
等の各種の基板などの光触媒材料担持体１上に担持され
ることにより、取り扱いやすい形態の光触媒体２０を構
成することができる。The photocatalyst material 10 of the present invention is carried on the photocatalyst material carrier 1 such as various substrates such as glass, metal, ceramics or fibers having a network structure, so that the photocatalyst body is easy to handle. 20 can be configured.
【００３９】[0039]
【作用】図１において、本発明の光触媒材料１０は、基
部２において光触媒材料担持体１の表面に固定されてい
て、該基部２から伸長する光触媒結晶体３および該基部
２の表面にはＰｔ等の貴金属の微粒子が担持された状態
となっている。光触媒結晶体３は柱状構造をとることに
よりその表面積が増大しており、既に光触媒機能が高活
性となっているが、その表面に貴金属微粒子が担持され
ていることによりアセトアルデヒド等の有機有害物質の
分解効率はさらに高くなり、貴金属微粒子を担持しない
場合と比較して、約２倍の分解効率が得られる。In FIG. 1, the photocatalyst material 10 of the present invention is fixed to the surface of the photocatalyst material carrier 1 at the base 2, and the photocatalyst crystal body 3 extending from the base 2 and Pt on the surface of the base 2. The fine particles of noble metal such as the above are supported. The surface area of the photocatalyst crystal body 3 is increased by taking a columnar structure, and the photocatalyst function is already highly active. However, since noble metal fine particles are carried on the surface of the photocatalyst crystal body 3, it is possible to prevent organic toxic substances such as acetaldehyde. The decomposition efficiency is further increased, and about twice as high as the decomposition efficiency obtained when no noble metal particles are supported.
【００４０】たとえば、本発明の光触媒材料１０におい
ては、触媒担持面積が７５ｍｍ×７５ｍｍの光触媒材料
担持体上に担持された担持量約０．１ｇの光触媒を用い
てなる該光触媒材料１０を用いてアセトアルデヒドガス
を分解させた場合に、容積２０Ｌ（リットル）のガラス
製容器中のアセトアルデヒドガス濃度を２０ｐｐｍから
１ｐｐｍ以下にするための所要時間を１０分間以下、さ
らには６分間にまで短縮することができる。貴金属微粒
子を担持しない場合であっても、従来の粉末状光触媒で
は約３０分間を要するところ、１５分程度で１ｐｐｍ以
下の濃度に達するため、該条件での分解効率は約２倍を
示し、相当の分解性能向上が達成されたのであるが、本
発明ではこれをさらに上回る分解性能が達成される。上
記条件で、本発明の光触媒材料を従来の粉末状光触媒と
比較すると、分解の所要時間は約４分の１から５分の１
程度にまで短縮され、約４倍ないし５倍の分解効率が得
られる。For example, in the photocatalyst material 10 of the present invention, the photocatalyst material 10 formed by using a photocatalyst having a carrying amount of about 0.1 g carried on a photocatalyst material carrier having a catalyst carrying area of 75 mm × 75 mm is used. When decomposing acetaldehyde gas, the time required to reduce the acetaldehyde gas concentration in a glass container having a volume of 20 L (liter) from 20 ppm to 1 ppm can be shortened to 10 minutes or less, and further to 6 minutes. . Even if the noble metal particles are not supported, the conventional powdery photocatalyst requires about 30 minutes, but since the concentration reaches 1 ppm or less in about 15 minutes, the decomposition efficiency under the conditions shows about twice, Although the improvement of the decomposition performance has been achieved, the decomposition performance further exceeding this is achieved in the present invention. Comparing the photocatalyst material of the present invention with the conventional powdery photocatalyst under the above conditions, the time required for the decomposition is about 1/4 to 1/5.
It is shortened to an extent and a decomposition efficiency of about 4 to 5 times is obtained.
【００４１】酸化チタン光触媒にＰｔ等の貴金属を担持
することにより光触媒機能が高活性になるのは、光触媒
への励起光の吸収により伝導帯に励起された励起電子が
貴金属微粒子上に集められプールされ、同時に正孔が光
触媒表面に吸着している有機有害物質に向かい移動する
ことによって、強制的に電子−正孔対の再結合確率が減
少する状態が形成されるためである。すなわち、電子−
正孔対の電荷分離状態の形成によりこれらの再結合が抑
制され、周囲の酸素および正孔による光触媒反応および
有機有害物質の酸化分解が促進されて、光触媒活性の高
感度化が達成されるものである。By supporting a noble metal such as Pt on the titanium oxide photocatalyst, the photocatalytic function becomes highly active because the excited electrons excited in the conduction band by the absorption of the exciting light into the photocatalyst are collected on the noble metal fine particles and pooled. At the same time, the holes move toward the organic harmful substance adsorbed on the surface of the photocatalyst, so that the recombination probability of the electron-hole pair is forcibly reduced. That is, electron-
The formation of the charge-separated state of the hole pair suppresses these recombination, promotes the photocatalytic reaction by ambient oxygen and holes and the oxidative decomposition of organic harmful substances, and achieves high photocatalytic activity. Is.
【００４２】図２は、本発明の光触媒材料製造方法の一
つについて、その構成を示すフロー図である。図におい
て本発明の製造方法は、貴金属がまだ表面に担持されて
いない状態の光触媒材料（原光触媒材料）を得るための
原光触媒材料作製工程Ｐ１と、該工程Ｐ１により得られ
た原光触媒材料の表面に貴金属微粒子を担持するための
貴金属担持工程Ｐ２とからなり、該貴金属担持工程Ｐ２
は、該原光触媒材料を貴金属化合物溶液に浸漬して貴金
属粒子を光触媒材料表面に吸着、担持する吸着工程Ｐ２
１と、該工程Ｐ２１において貴金属が吸着、担持された
光触媒材料を乾燥し次いで熱処理する乾燥熱処理工程Ｐ
２２と、から構成される。FIG. 2 is a flow chart showing the structure of one of the methods for producing a photocatalyst material of the present invention. In the figure, the production method of the present invention shows a raw photocatalyst material preparation step P1 for obtaining a photocatalyst material (raw photocatalyst material) in which no precious metal is not yet supported on the surface, and a raw photocatalyst material preparation step P1 obtained by the step P1. A noble metal supporting step P2 for supporting fine particles of noble metal on the surface, and the noble metal supporting step P2
Is an adsorption step P2 in which the raw photocatalyst material is immersed in a precious metal compound solution to adsorb and carry the precious metal particles on the surface of the photocatalyst material.
1 and a dry heat treatment step P in which the photocatalyst material on which the noble metal is adsorbed and supported in step P21 is dried and then heat-treated.
22 and.
【００４３】図において本製造方法では、前記乾燥熱処
理工程Ｐ２２の後に、前記光触媒材料表面に担持された
酸化状態の貴金属微粒子を還元するための還元工程Ｐ２
３を設けることができる。In the figure, in the present manufacturing method, after the dry heat treatment step P22, a reducing step P2 for reducing the oxidized noble metal fine particles carried on the surface of the photocatalytic material.
3 can be provided.
【００４４】図において本製造方法では、前記貴金属化
合物としてヘキサクロロ白金（VI）酸六水和物（以下、
「Ｈ２ＰｔＣｌ６・６Ｈ２Ｏ」とも記載する。）等の白
金を含む化合物を用いることとすることができる。白金
を含む化合物としては、溶液を調製することができるも
のである限り、この他にも各種のものを用いることがで
きる。In the figure, in the present production method, hexachloroplatinic (VI) acid hexahydrate (hereinafter, referred to as the noble metal compound)
It is also described as “H 2 PtCl 6 · 6H 2 O”. ) And other platinum-containing compounds can be used. As the platinum-containing compound, various compounds other than the above can be used as long as a solution can be prepared.
【００４５】[0045]
【作用】図において本発明の光触媒材料製造方法では、
原光触媒材料作製工程Ｐ１において貴金属がまだ表面に
担持されていない状態の光触媒材料（原光触媒材料）が
得られ、次いで貴金属担持工程Ｐ２において該工程Ｐ１
により得られた原光触媒材料の表面に、ヘキサクロロ白
金（VI）酸六水和物等白金を含む化合物など貴金属微粒
子が担持されるが、該貴金属担持工程Ｐ２のうち吸着工
程Ｐ２１において該原光触媒材料は貴金属化合物溶液に
浸漬されて貴金属粒子が光触媒材料表面に吸着、担持さ
れ、次いで乾燥熱処理工程Ｐ２２において該工程Ｐ２１
で貴金属が吸着、担持された光触媒材料が乾燥され次い
で熱処理されて、本発明の貴金属微粒子が担持された柱
状構造の光触媒材料が製造される。In the figure, in the method for producing a photocatalyst material of the present invention,
In the raw photocatalyst material preparation step P1, a photocatalyst material (raw photocatalyst material) in which no precious metal is not yet supported on the surface is obtained, and then in the precious metal supporting step P2, the step P1
The noble metal fine particles such as a compound containing platinum such as hexachloroplatinum (VI) acid hexahydrate are supported on the surface of the raw photocatalytic material obtained by the above. The raw photocatalytic material in the adsorption step P21 of the noble metal supporting step P2. Is immersed in a noble metal compound solution so that the noble metal particles are adsorbed and supported on the surface of the photocatalyst material, and then in the dry heat treatment step P22, the step P21 is performed.
The photocatalyst material on which the noble metal is adsorbed and carried is dried and then heat-treated to produce the photocatalyst material of the present invention having a columnar structure carrying the noble metal fine particles.
【００４６】前記乾燥熱処理工程Ｐ２２を経ることによ
って、貴金属微粒子を担持しない柱状構造の光触媒材料
よりも光触媒機能が高活性化した本発明の光触媒材料を
製造することができるが、さらに該工程Ｐ２２の後に還
元工程Ｐ２３を設けてこれを経ることによって、前記光
触媒材料表面に担持された酸化状態の貴金属微粒子は還
元され、光触媒機能をさらに高活性化することができ
る。By passing through the dry heat treatment step P22, the photocatalyst material of the present invention having a higher photocatalytic function than the photocatalyst material having a columnar structure which does not carry the noble metal fine particles can be produced. By subsequently providing the reduction step P23 and passing through it, the oxidized precious metal fine particles carried on the surface of the photocatalytic material are reduced, and the photocatalytic function can be further activated.
【００４７】図３は、本発明の他の光触媒材料製造方法
について、その構成を示すフロー図である。図において
本発明の製造方法は、貴金属がまだ表面に担持されてい
ない状態の光触媒材料（以下、「原光触媒材料」ともい
う。）を得るための原光触媒材料作製工程Ｐ１と、該工
程Ｐ１により得られた原光触媒材料の表面に貴金属微粒
子を担持するための貴金属担持工程Ｐ３とからなり、該
貴金属担持工程Ｐ３は、スパッタリング法、真空蒸着
法、またはその他のＰＶＤ法により原光触媒材料の表面
に貴金属微粒子を担持させるＰＶＤ工程Ｐ３である。し
たがって本方法では、原光触媒材料作製工程Ｐ１におい
て貴金属がまだ表面に担持されていない状態の光触媒材
料（原光触媒材料）が得られ、ＰＶＤ工程Ｐ３において
該原光触媒材料の表面に貴金属微粒子が担持されて、本
発明の光触媒材料が製造される。FIG. 3 is a flow chart showing the structure of another method for producing a photocatalyst material according to the present invention. In the figure, the production method of the present invention comprises a raw-photocatalyst-material producing step P1 for obtaining a photocatalyst material (hereinafter, also referred to as "raw-photocatalyst material") in a state in which a noble metal is not yet supported on the surface, and a step P1. And a noble metal supporting step P3 for supporting the noble metal fine particles on the surface of the obtained raw photocatalytic material. The noble metal supporting step P3 is performed on the surface of the raw photocatalytic material by a sputtering method, a vacuum deposition method, or another PVD method. This is the PVD step P3 of supporting the noble metal particles. Therefore, in this method, a photocatalyst material (raw photocatalyst material) in which no precious metal is not yet supported on the surface is obtained in the raw photocatalyst material preparation step P1, and the precious metal fine particles are loaded on the surface of the raw photocatalyst material in the PVD step P3. Thus, the photocatalytic material of the present invention is manufactured.
【００４８】前記ＰＶＤ工程Ｐ３において原光触媒材料
に蒸着、担持させることのできる貴金属としては、Ｐｔ
を始めとして、Ｐｄ、Ａｕ、Ａｇなど各種の貴金属を用
いることができる。In the PVD step P3, Pt is a noble metal that can be deposited and supported on the raw photocatalytic material.
In addition, various noble metals such as Pd, Au and Ag can be used.
【００４９】図４は、図２および図３における原光触媒
材料作製工程Ｐ１の構成を示すフロー図である。図４に
おいて、図２および図３における原光触媒材料作製工程
Ｐ１は、光触媒材料１０の基部１とするための結晶核Ｓ
１を、有機金属化合物または無機金属化合物を含むゾル
溶液Ｓ２に浸漬し、または光触媒材料１０の基部１とす
るための結晶核Ｓ１に有機金属化合物または無機金属化
合物を含むゾル溶液Ｓ２を塗布して、ゲル化による光触
媒材料の原型Ｍ３を得るためのゲル化工程３１と、該ゲ
ル化工程３１により得られた該原型Ｍ３を乾燥して固化
し、固化した原型Ｍ４を得るための固化工程３２と、該
固化した原型Ｍ４を熱処理して、柱状構造または柱状中
空構造をとる光触媒結晶体３を有する原光触媒材料Ｍ５
を得るための熱処理工程３３と、から主として構成され
る。FIG. 4 is a flow chart showing the structure of the raw photocatalyst material producing step P1 shown in FIGS. In FIG. 4, the raw photocatalyst material producing step P1 in FIGS.
1 is immersed in a sol solution S2 containing an organometallic compound or an inorganic metal compound, or the crystal nucleus S1 for forming the base 1 of the photocatalyst material 10 is coated with a sol solution S2 containing an organometallic compound or an inorganic metal compound. A gelling step 31 for obtaining a prototype M3 of a photocatalytic material by gelling, and a solidification step 32 for obtaining a solidified prototype M4 by drying and solidifying the prototype M3 obtained by the gelling step 31. , The raw photocatalytic material M5 having a photocatalytic crystal body 3 having a columnar structure or a columnar hollow structure by heat-treating the solidified prototype M4
And a heat treatment step 33 for obtaining
【００５０】図において、ゲル化工程３１により、光触
媒材料１０の基部１とするための結晶核Ｓ１は、有機金
属化合物または無機金属化合物を含むゾル溶液Ｓ２に浸
漬され、または光触媒材料１０の基部１とするための結
晶核Ｓ１に有機金属化合物または無機金属化合物を含む
ゾル溶液Ｓ２が塗布されて、ゲル化による光触媒材料の
原型Ｍ３が得られ、次いで固化工程３２により、該ゲル
化工程３１により得られた該原型Ｍ３は乾燥されて固化
し、固化した原型Ｍ４が得られ、次いで熱処理工程３３
により、該固化した原型Ｍ４は熱処理されて、柱状構造
または柱状中空構造をとる光触媒結晶体３を有する原光
触媒材料Ｍ５が得られる。In the figure, by the gelling step 31, the crystal nucleus S1 for forming the base 1 of the photocatalyst material 10 is immersed in the sol solution S2 containing the organometallic compound or the inorganic metal compound, or the base 1 of the photocatalyst material 10 is formed. The sol solution S2 containing an organometallic compound or an inorganic metal compound is applied to the crystal nucleus S1 for obtaining a prototype M3 of the photocatalytic material by gelation, and then a solidification step 32 and a gelation step 31 The obtained prototype M3 is dried and solidified to obtain a solidified prototype M4, which is then subjected to a heat treatment step 33.
Thus, the solidified prototype M4 is heat-treated to obtain the raw photocatalytic material M5 having the photocatalytic crystal body 3 having a columnar structure or a columnar hollow structure.
【００５１】図５は、上述した本発明に係る二通りの光
触媒材料製造方法によりＰｔを担持する例について、そ
の工程を示したフロー図である。図において湿式法とし
て示される貴金属化合物溶液を用いる方法では、柱状酸
化チタン光触媒はヘキサクロロ白金（VI）酸六水和物溶
液に浸漬され、次いで１５０℃で６０分間乾燥され、次
いで大気中において４５０℃で１２０分間熱処理され、
次いで選択的に４５０℃雰囲気中で１２０分間水素還元
処理され、Ｐｔ担持柱状酸化チタン光触媒が作製され
る。これは、出発原料である柱状酸化チタン光触媒に比
べ、約２倍の分解性能を示す。FIG. 5 is a flow chart showing the steps of an example of carrying Pt by the above-described two methods for producing a photocatalyst material according to the present invention. In the method using a noble metal compound solution shown as a wet method in the figure, the columnar titanium oxide photocatalyst is immersed in a hexachloroplatinum (VI) acid hexahydrate solution, then dried at 150 ° C. for 60 minutes, and then 450 ° C. in the atmosphere. Heat treated for 120 minutes at
Then, the Pt-supported columnar titanium oxide photocatalyst is prepared by selectively performing hydrogen reduction treatment for 120 minutes in an atmosphere of 450 ° C. This shows about twice the decomposition performance of the columnar titanium oxide photocatalyst, which is the starting material.
【００５２】図において一方、物理的蒸着法（ＰＶＤ
法）では、柱状酸化チタン光触媒はスパッタ法によりＰ
ｔ微粒子が担持され、Ｐｔ担持柱状酸化チタン光触媒が
作製される。これは、出発原料である柱状酸化チタン光
触媒に比べ、約２倍の分解性能を示す。On the other hand, in the figure, the physical vapor deposition method (PVD
Method), columnar titanium oxide photocatalysts are
The fine particles of t are supported, and a Pt-supported columnar titanium oxide photocatalyst is produced. This shows about twice the decomposition performance of the columnar titanium oxide photocatalyst, which is the starting material.
【００５３】図５の湿式法により、Ｐｔを担持させた柱
状構造光触媒材料を作製する方法について、さらに詳細
に説明する。
＜原光触媒材料の作製＞まず本発明で出発原料とする、
貴金属がまだ担持されていない柱状構造光触媒材料は、
有機金属化合物、または無機金属化合物を用いて作製す
ることができる。有機金属化合物を用いて作製する場合
は、有機金属化合物から成るゾル溶液中に結晶核を入
れ、または結晶核にゾル溶液を塗布し、固化、熱処理を
施すことにより、結晶核上に柱状構造または柱状中空構
造を有する酸化チタン結晶を、ガラス、金属、セラミッ
クスまたは網目状構造を有する繊維等の各種の基板など
の光触媒材料担持体表面において形成する。The method for producing the Pt-supported columnar structure photocatalytic material by the wet method shown in FIG. 5 will be described in more detail. <Preparation of raw photocatalyst material> First, the starting material in the present invention,
The columnar structure photocatalyst material on which the noble metal is not yet supported is
It can be manufactured using an organic metal compound or an inorganic metal compound. In the case of using an organometallic compound, a crystal nucleus is placed in a sol solution composed of an organometallic compound, or a sol solution is applied to the crystal nucleus, and solidification and heat treatment are performed to form a columnar structure or a crystal structure on the crystal nucleus. Titanium oxide crystals having a columnar hollow structure are formed on the surface of a photocatalyst material carrier such as glass, metal, ceramics or various substrates such as fibers having a network structure.
【００５４】すなわち、有機金属化合物からなるゾル溶
液は、有機溶媒、水、酸を混合し調製した溶液に、チタ
ニウムテトライソプロポキシド（以下、「ＴＴＩＰ」と
もいう。）等の有機金属化合物を攪拌しながら滴下、混
合して得る。That is, the sol solution consisting of an organometallic compound is prepared by mixing an organic solvent, water and an acid, and stirring an organometallic compound such as titanium tetraisopropoxide (hereinafter also referred to as "TTIP"). While dropping, mix and obtain.
【００５５】このようにして得たゾル溶液中に、各種作
製法により作製した結晶核を浸漬し、または各種作製法
により作製した結晶核に前記のようにして得たゾル溶液
を塗布し、乾燥固化、熱処理を施すことにより、結晶核
上に酸化チタン結晶を形成する。一例として、固化は到
達温度１５０℃〜２００℃、保持時間２時間の条件で、
また熱処理は電気炉中で昇温速度１０℃／ｍｉｎ、到達
温度５００℃〜６００℃、保持時間２時間の条件で、そ
れぞれ行うことができる。The crystal nuclei produced by various production methods are dipped in the sol solution thus obtained, or the sol solution obtained as described above is applied to the crystal nuclei produced by various production methods and dried. By solidifying and heat-treating, a titanium oxide crystal is formed on the crystal nucleus. As an example, solidification is achieved under the conditions of an ultimate temperature of 150 ° C to 200 ° C and a holding time of 2 hours,
The heat treatment can be carried out in an electric furnace under the conditions of a temperature rising rate of 10 ° C./min, an ultimate temperature of 500 ° C. to 600 ° C., and a holding time of 2 hours.
【００５６】各種作製法が可能な結晶核の作製のうち、
噴霧熱分解法（以下、「ＳＰＤ法」ともいう。）による
酸化チタン結晶膜の作製は、本願発明者らによる非公知
の特許出願（特願２００１−１８１９６９等）に示され
ている方法に従えば、ＴＴＩＰ等の有機金属化合物に有
機溶媒を加えて原料液とし、これを噴霧熱分解（ＳＰ
Ｄ）装置を用いて、基板等の光触媒材料担持体に噴霧す
ることにより行う。具体的な作製例を挙げると、たとえ
ば原料液としては、ＴＴＩＰにアセチルアセトン（以
下、「Ｈａｃａｃ」と記す。）をｍｏｌ比（Ｈａｃａｃ
／ＴＴＩＰ）１．０で添加し、これをイソプロピルアル
コールで希釈し、攪拌することによって調製する。ＳＰ
Ｄ装置による成膜条件は、噴霧圧力０．３ＭＰａ、噴霧
量１．０ｍｌ／ｓｅｃ、噴霧時間０．５ｍｌ／回、基板
温度４５０℃、噴霧回数２００回、とすることにより、
走査型電子顕微鏡（以下、「ＳＥＭ」と記す。）による
表面観察上、大きさ３０ｎｍ〜１００ｎｍの結晶から構
成される酸化チタン結晶膜を、本発明の光触媒材料の出
発原料を構成するための結晶核すなわち基部として得る
ことができる。Among the production of crystal nuclei capable of various production methods,
Preparation of a titanium oxide crystal film by a spray pyrolysis method (hereinafter, also referred to as “SPD method”) may be performed according to a method disclosed in an unknown patent application (Japanese Patent Application No. 2001-181969 etc.) filed by the present inventors. For example, an organic solvent is added to an organic metal compound such as TTIP to prepare a raw material liquid, which is spray pyrolyzed (SP
D) Spraying is carried out on a photocatalyst material carrier such as a substrate using a device. As a specific production example, for example, as a raw material liquid, TTIP is mixed with acetylacetone (hereinafter referred to as “Hacac”) in a molar ratio (Hacac).
/ TTIP) 1.0, which is diluted with isopropyl alcohol and prepared by stirring. SP
The film forming conditions by the D device are as follows: spray pressure 0.3 MPa, spray amount 1.0 ml / sec, spray time 0.5 ml / time, substrate temperature 450 ° C., spray frequency 200 times.
On observation of the surface with a scanning electron microscope (hereinafter referred to as "SEM"), a titanium oxide crystal film composed of crystals having a size of 30 nm to 100 nm is used as a starting material for the photocatalyst material of the present invention. It can be obtained as a core or base.
【００５７】＜担持する貴金属の原料溶液＞Ｐｔ化合物
としてヘキサクロロ白金（VI）酸六水和物を用いる場
合、これを水で希釈し、吸着に適する濃度のＰｔ溶液を
調製する。濃度は、たとえば２×１０ −３ｍｏｌ／Ｌ
（リットル）に調整して用いることができる。<Raw material solution of precious metal to be supported> Pt compound
When hexachloroplatinum (VI) acid hexahydrate is used as
If this is the case, dilute it with water and add a Pt solution with a concentration suitable for adsorption.
Prepare. The concentration is, for example, 2 × 10 -3mol / L
It can be adjusted to (liter) and used.
【００５８】原料溶液濃度は、２×１０−５ｍｏｌ／Ｌ
（リットル）程度以上のものから用いることができる。
溶液濃度が低く、原料溶液が希薄であるほど、原光触媒
材料の表面に担持される金属の粒子径を微粒子化するこ
とができ、光触媒機能向上の効果が得られる。したがっ
て、溶液濃度を変化させることにより光触媒材料のＰｔ
等貴金属微粒子の粒子径を１〜数十ｎｍ程度の範囲で制
御することが可能と考えられる。The raw material solution concentration was 2 × 10 −5 mol / L.
It is possible to use from those of about (liter) or more.
The lower the solution concentration and the thinner the raw material solution, the finer the particle size of the metal supported on the surface of the raw photocatalytic material, and the effect of improving the photocatalytic function can be obtained. Therefore, by changing the solution concentration, Pt of the photocatalytic material
It is considered possible to control the particle size of the noble metal fine particles in the range of 1 to several tens of nm.
【００５９】＜吸着工程−白金吸着法＞Ｐｔ溶液中に、
原光触媒材料（柱状構造または柱状中空構造の酸化チタ
ン光触媒材料）が担持体上に担持された光触媒体を浸漬
し、溶液中のＰｔを酸化チタン表面に、平衡濃度に達す
るまで吸着させる（平衡吸着法）。なお、過剰濃度のＰ
ｔは吸着されない。<Adsorption Step-Platinum Adsorption Method> In a Pt solution,
The photocatalyst material in which the original photocatalyst material (titanium oxide photocatalyst material of columnar structure or columnar hollow structure) is supported is immersed, and Pt in the solution is adsorbed on the titanium oxide surface until the equilibrium concentration is reached (equilibrium adsorption). Law). It should be noted that excessive concentration of P
t is not adsorbed.
【００６０】Ｐｔを原光触媒材料上に吸着、担持させる
には、前記平衡吸着法の他にイオン交換法等、適宜の吸
着手法により行うことも可能である。In order to adsorb and support Pt on the raw photocatalytic material, it is possible to carry out an appropriate adsorption method such as an ion exchange method in addition to the equilibrium adsorption method.
【００６１】＜乾燥熱処理工程＞原光触媒材料にＰｔを
担持した後、光触媒体を水で洗浄し、原光触媒材料表面
の余剰のＰｔ溶液を除去する。その後光触媒体を、１５
０℃で１時間等の適宜の条件で乾燥させる。次いで光触
媒体を、空気中にて４５０℃で２時間等の適宜の条件に
より、熱処理する。なお、水洗浄工程は省略することが
できる。<Dry Heat Treatment Step> After supporting Pt on the raw photocatalyst material, the photocatalyst is washed with water to remove the excess Pt solution on the surface of the raw photocatalyst material. Then, the photocatalyst was
It is dried under appropriate conditions such as 0 ° C. for 1 hour. Next, the photocatalyst is heat-treated in the air under appropriate conditions such as 450 ° C. for 2 hours. The water washing step can be omitted.
【００６２】＜還元工程＞酸化チタン光触媒にＰｔを担
持し、空気中で熱処理した状態では、Ｐｔ表面は酸化状
態にある。これを水素雰囲気中で還元する。たとえば石
英ガラス管に光触媒体を充填して、４５０℃で２時間、
水素−アルゴン混合ガスや純水素ガスを用いる、等の適
宜の条件により、還元処理を行うことができる。以上の
処理を経て、湿式法による、Ｐｔを担持させた柱状構造
光触媒材料を作製することができる。<Reduction Step> When Pt is supported on the titanium oxide photocatalyst and heat-treated in air, the Pt surface is in an oxidized state. This is reduced in a hydrogen atmosphere. For example, fill a quartz glass tube with a photocatalyst, and heat it at 450 ° C for 2 hours.
The reduction treatment can be performed under appropriate conditions such as using a hydrogen-argon mixed gas or pure hydrogen gas. Through the above treatment, a columnar structure photocatalyst material supporting Pt can be manufactured by a wet method.
【００６３】[0063]
【実施例】以下、実施例と比較例による試験結果につい
て説明するが、本発明は以下の実施例に限定されるもの
ではない。EXAMPLES The test results of Examples and Comparative Examples will be described below, but the present invention is not limited to the following Examples.
【００６４】＜結晶核、柱状構造光触媒材料の作製＞中
性洗剤、イソプロピルアルコール、純水で洗浄処理を施
した、無アルカリガラス、およびシリカ繊維フィルター
（アドバンテック製 ＱＲ−１００）を基板として用
い、その基板表面において、有機金属化合物から成るゾ
ル溶液中に結晶核を入れ、または結晶核にゾル溶液を塗
布し、固化、熱処理を施すことにより、結晶核上に柱状
中空構造を有する酸化チタン結晶を形成し、それぞれ酸
化チタン基板、および酸化チタンフィルターとした。触
媒担持面積は７５ｍｍ×７５ｍｍとし、酸化チタン担持
量は約０．１ｇとした。なお以下においても、同様の触
媒担持面積および酸化チタン担持量とした。<Preparation of Crystal Nucleus and Photocatalyst Material with Columnar Structure> Alkali-free glass washed with neutral detergent, isopropyl alcohol and pure water, and silica fiber filter (QR-100 manufactured by Advantech) were used as substrates. On the surface of the substrate, crystal nuclei were put into a sol solution composed of an organometallic compound, or the sol solution was applied to the crystal nuclei, solidified, and subjected to heat treatment to obtain titanium oxide crystals having a columnar hollow structure on the crystal nuclei. They were formed into a titanium oxide substrate and a titanium oxide filter, respectively. The catalyst supporting area was 75 mm × 75 mm, and the titanium oxide supporting amount was about 0.1 g. In the following, the same catalyst supporting area and titanium oxide supporting amount were used.
【００６５】有機金属化合物からなるゾル溶液の調整方
法としては、１，３−ブタンジオール：３５ｇ、Ｈ２
Ｏ：０．４ｇ、硝酸：０．５ｇを混合して溶液とし、こ
の溶液にチタニウムテトライソプロポキシド(以下、
「ＴＴＩＰ」と記す。)５ｇを攪拌しながら滴下し、そ
の後４時間常温にて攪拌しゾル溶液を得た。As a method for preparing a sol solution containing an organometallic compound, 1,3-butanediol: 35 g, H 2
O: 0.4 g and nitric acid: 0.5 g were mixed to form a solution, and titanium tetraisopropoxide (hereinafter,
It is written as "TTIP". ) 5 g was added dropwise with stirring, and then the mixture was stirred for 4 hours at room temperature to obtain a sol solution.
【００６６】このようにして得たゾル溶液中に、各種作
製法により作製した結晶核を浸漬し、または各種作製法
により作製した結晶核に前記のようにして得たゾル溶液
を塗布し、乾燥固化、熱処理を施すことにより、結晶核
上に酸化チタン結晶を形成した。固化は乾燥機中で到達
温度１５０℃〜２００℃、保持時間２時間の条件で行っ
た。熱処理は電気炉中で昇温速度１０℃／ｍｉｎ、到達
温度５００℃〜６００℃、保持時間２時間の条件で行っ
た。The crystal nuclei prepared by various preparation methods are dipped in the sol solution thus obtained, or the sol solution obtained as described above is applied to the crystal nuclei prepared by various preparation methods and dried. Titanium oxide crystals were formed on the crystal nuclei by solidification and heat treatment. The solidification was carried out in a dryer under the conditions that the ultimate temperature was 150 ° C to 200 ° C and the holding time was 2 hours. The heat treatment was performed in an electric furnace under the conditions of a temperature rising rate of 10 ° C./min, an ultimate temperature of 500 ° C. to 600 ° C., and a holding time of 2 hours.
【００６７】各種作製法による結晶核の作製のうち、Ｓ
ＰＤ法による酸化チタン結晶膜の作製方法は、本願発明
者らによる非公知の特許出願（特願２００１−１８１９
６９等）に示されている方法に従い、次のように調製し
た。すなわち、原料液は、ＴＴＩＰにアセチルアセトン
（以下、「Ｈａｃａｃ」と記す。）をｍｏｌ比（Ｈａｃ
ａｃ／ＴＴＩＰ）１．０で添加し、これをイソプロピル
アルコールで希釈し、攪拌することによって調製した。
噴霧熱分解（ＳＰＤ）装置（(株)メイク製 ＹＫII）に
よる成膜条件は、噴霧圧力０．３ＭＰａ、噴霧量１．０
ｍｌ／ｓｅｃ、噴霧時間０．５ｍｌ／回、基板温度４５
０℃、噴霧回数２００回、で行った。ＳＰＤ法により作
製した酸化チタン結晶膜は、走査型電子顕微鏡（以下、
「ＳＥＭ」と記す。）による表面観察により、大きさ３
０ｎｍ〜１００ｎｍの結晶から構成されていることが確
認された。Of the production of crystal nuclei by various production methods, S
The method of forming a titanium oxide crystal film by the PD method is an unknown patent application by the present inventors (Japanese Patent Application No. 2001-1819).
69 etc.) and prepared as follows. That is, in the raw material liquid, TTIP was mixed with acetylacetone (hereinafter referred to as “Hacac”) in a molar ratio (Hac
ac / TTIP) 1.0, which was diluted with isopropyl alcohol and prepared by stirring.
The film formation conditions using a spray pyrolysis (SPD) device (YKII manufactured by Make Co., Ltd.) are as follows: spray pressure 0.3 MPa, spray amount 1.0
ml / sec, spraying time 0.5 ml / time, substrate temperature 45
It was carried out at 0 ° C. and 200 times of spraying. The titanium oxide crystal film produced by the SPD method is a scanning electron microscope (hereinafter,
It is written as "SEM". ), The size is 3
It was confirmed to be composed of crystals of 0 nm to 100 nm.
【００６８】＜湿式法による貴金属の担持＞
１．担持する貴金属の原料溶液
ヘキサクロロ白金（VI）酸六水和物（Ｈ２ＰｔＣｌ６・
６Ｈ２Ｏ、関東化学製・特級）を蒸留水で希釈し、濃度
を２×１０−３ｍｏｌ／Ｌ（リットル）に調整した。<Supporting Noble Metal by Wet Method> Raw material solution of precious metal to be supported Hexachloroplatinic (VI) acid hexahydrate (H 2 PtCl 6 ·
6H 2 O, special grade manufactured by Kanto Kagaku) was diluted with distilled water to adjust the concentration to 2 × 10 −3 mol / L (liter).
【００６９】２．吸着工程−白金吸着法
Ｐｔ溶液中に、原酸化チタン光触媒材料が担持されてな
る上記酸化チタン基板、および酸化チタンフィルターを
浸漬し、２４時間放置した。この操作により溶液中のＰ
ｔを酸化チタン表面に、平衡濃度に達するまで吸着させ
た。2. Adsorption Step-Platinum Adsorption Method The titanium oxide substrate carrying the raw titanium oxide photocatalyst material and the titanium oxide filter were immersed in a Pt solution and left for 24 hours. By this operation, P in the solution
t was adsorbed on the surface of titanium oxide until an equilibrium concentration was reached.
【００７０】３．乾燥熱処理工程
酸化チタン基板、および酸化チタンフィルターにＰｔを
担持した後、これらを純水で洗浄し、原光触媒材料表面
の余剰のＰｔ溶液を除去した。その後、１５０℃で１時
間乾燥させ、次いで空気中にて４５０℃で２時間熱処理
した。3. Drying heat treatment step After supporting Pt on the titanium oxide substrate and the titanium oxide filter, these were washed with pure water to remove the excess Pt solution on the surface of the raw photocatalytic material. Then, it was dried at 150 ° C. for 1 hour and then heat-treated in air at 450 ° C. for 2 hours.
【００７１】４．還元工程
酸化チタン光触媒にＰｔを担持し、空気中で熱処理した
状態では、Ｐｔ表面は酸化状態にあるため、これを水素
雰囲気中で還元した。石英ガラス管に酸化チタン基板、
および酸化チタンフィルターを充填して、４５０℃で２
時間、１０容量％水素−アルゴン混合ガスで還元処理し
た。4. Reduction step In the state where Pt was supported on the titanium oxide photocatalyst and heat-treated in air, the Pt surface was in an oxidized state, so this was reduced in a hydrogen atmosphere. Titanium oxide substrate on quartz glass tube,
And fill the titanium oxide filter, 2 at 450 ℃
For a period of time, reduction treatment was performed with a 10 vol% hydrogen-argon mixed gas.
【００７２】＜実施例１ 湿式法によるＰｔ担持光触媒
材料＞上述の湿式法により、柱状中空酸化チタン光触媒
材料にＰｔを担持させ、本実施例の酸化チタン基板、お
よび酸化チタンフィルター（以下、「酸化チタン基板
等」という。）を作製した。ただし還元工程の処理は行
わなかった。得られた光触媒材料は、柱状中空構造の酸
化チタン結晶表面に粒径１〜５０ｎｍ程度のＰｔ微粒子
が担持されていると予想される。<Example 1 Pt-supported photocatalyst material by wet method> Pt was supported on the columnar hollow titanium oxide photocatalyst material by the above-mentioned wet method, and the titanium oxide substrate of this example and the titanium oxide filter (hereinafter referred to as "oxidation") were used. A titanium substrate, etc. ”was produced. However, the reduction process was not performed. It is expected that the obtained photocatalyst material has Pt particles having a particle size of about 1 to 50 nm supported on the surface of the titanium oxide crystal having a columnar hollow structure.
【００７３】＜実施例２ 還元工程を含む湿式法による
Ｐｔ担持光触媒材料＞上述の湿式法により、柱状中空酸
化チタン光触媒材料にＰｔを担持させ、本実施例の酸化
チタン基板等を作製した。本実施例では還元工程の処理
を行った。得られた光触媒材料は、柱状中空構造の酸化
チタン結晶表面に粒径１〜５０ｎｍ程度のＰｔ微粒子が
担持されていると予想される。Example 2 Pt-supporting photocatalytic material by a wet method including a reduction step> Pt was supported on a columnar hollow titanium oxide photocatalyst material by the above-mentioned wet method to prepare a titanium oxide substrate or the like of this example. In this example, the reduction process was performed. It is expected that the obtained photocatalyst material has Pt particles having a particle size of about 1 to 50 nm supported on the surface of the titanium oxide crystal having a columnar hollow structure.
【００７４】＜実施例３ ＰＶＤ法によるＰｔ担持光触
媒材料＞ＰＶＤ法により、柱状中空酸化チタン光触媒材
料にＰｔを担持させ、本実施例の酸化チタン基板、およ
び酸化チタンフィルターを作製した。ＲＦマグネトロン
スパッタリング装置（日本真空技術(株)、ＳＨ−３５０
ＥＬ−Ｔ０６）を用いたスパッタ法により行った。成膜
室内に柱状中空構造の酸化チタン光触媒材料が担持され
てなる前記酸化チタン基板等を、Ｐｔターゲットに対向
させて載置した。ターゲットは、ターゲット純度９９．
９９％以上のＰｔターゲットを用いた。油回転ポンプに
より成膜室内を１０Ｐａまで排気した後、ターボ分子ポ
ンプで排気を行い、成膜室内を所定の真空度にした。次
いで、純度９９．９９９％以上のアルゴンガスを導入し
て成膜室内をアルゴン雰囲気とした。このとき、所定の
アルゴンガス圧力（スパッタ圧力）になるように、導入
ガス流量とメインバルブの開閉度を調節した。そして直
流電源によりＰｔターゲットに電力を印加してＰｔのス
パッタリングを行い、載置された酸化チタン基板等を回
転速度３ｒｐｍで回転させながら、その表面にＰｔ微粒
子を担持させた。Ｐｔ膜の形成ではなくＰｔ微粒子の担
持が目的なので、３分間の短時間で処理を行った。得ら
れた光触媒材料は、柱状中空構造の酸化チタン結晶表面
に粒径１〜５０ｎｍ程度のＰｔ微粒子が担持されている
と予想される。Example 3 Pt-supporting photocatalyst material by PVD method Pt was supported on a columnar hollow titanium oxide photocatalyst material by PVD method to prepare a titanium oxide substrate and a titanium oxide filter of this example. RF magnetron sputtering system (Japan Vacuum Technology Co., Ltd., SH-350
It was performed by a sputtering method using EL-T06). The titanium oxide substrate on which the titanium oxide photocatalyst material having a columnar hollow structure was carried was placed in the film forming chamber so as to face a Pt target. The target has a target purity of 99.
99% or more of Pt target was used. After the film-forming chamber was evacuated to 10 Pa by an oil rotary pump, it was evacuated by a turbo-molecular pump to bring the film-forming chamber to a predetermined vacuum degree. Next, an argon gas having a purity of 99.999% or higher was introduced to make the inside of the film formation chamber an argon atmosphere. At this time, the flow rate of the introduced gas and the degree of opening / closing of the main valve were adjusted so that a predetermined argon gas pressure (sputtering pressure) was obtained. Then, electric power was applied to the Pt target by a DC power source to perform sputtering of Pt, and the Pt fine particles were carried on the surface of the mounted titanium oxide substrate or the like while rotating at a rotation speed of 3 rpm. Since the purpose is not to form a Pt film but to support Pt fine particles, the treatment is performed in a short time of 3 minutes. It is expected that the obtained photocatalyst material has Pt particles having a particle size of about 1 to 50 nm supported on the surface of the titanium oxide crystal having a columnar hollow structure.
【００７５】＜比較例１ Ｐｔ担持しない柱状中空構造
光触媒材料＞上述のＰｔ微粒子担持処理を施さない柱状
中空構造の酸化チタン基板等を比較例１とした。Comparative Example 1 Pt-supported columnar hollow structure photocatalytic material> The above-mentioned columnar hollow-structure titanium oxide substrate not subjected to the Pt fine particle support treatment was used as Comparative Example 1.
【００７６】＜比較例２ 市販の粉末状光触媒材料＞市
販の粉末状光触媒材料（日本アエロジル製 Ｐ−２５）
を比較例２とした。ＳＥＭを用いた表面観察では、これ
は、粒径２０〜３０ｎｍ程度の酸化チタン粒子から構成
されていた。Comparative Example 2 Commercially available powdery photocatalytic material> Commercially available powdery photocatalytic material (P-25 manufactured by Nippon Aerosil Co., Ltd.)
Was set as Comparative Example 2. According to the surface observation using SEM, it was composed of titanium oxide particles having a particle diameter of about 20 to 30 nm.
【００７７】表１に各実施例および比較例の作製法概要
を示す。Table 1 shows the outline of the production method of each example and comparative example.
【００７８】[0078]
【表１】 [Table 1]
【００７９】＜特性評価方法＞光触媒機能の評価とし
て、有害物質であるアセトアルデヒドの分解試験を実施
した。試験方法は、まず、作製した酸化チタン光触媒体
（触媒担持面積７５ｍｍ×７５ｍｍ、酸化チタン担持量
約０．１ｇ）を容積２０Ｌ（リットル）のガラス製の容
器に入れ、容器内を人工空気で置換したのち、アセトア
ルデヒドガスを２０ｐｐｍとなるように容器内に注入し
た。次に、波長２５４ｎｍの殺菌灯を酸化チタン光触媒
体に照射し、容器内のアセトアルデヒド濃度が１ｐｐｍ
以下になるまでに要する時間をガスモニターにて測定し
た。作製した酸化チタン光触媒体の表面観察は、ＳＥＭ
により行った。用いた人工空気（日本酸素(株)製）のガ
ス組成は、窒素７８％、酸素２１％、アルゴン０．９
％、炭酸ガス（ＣＯ、ＣＯ２、ＣＨ４）０．０３％、残
りは水分である。<Characteristic Evaluation Method> As an evaluation of the photocatalytic function, a decomposition test of acetaldehyde which is a harmful substance was carried out. In the test method, first, the prepared titanium oxide photocatalyst body (catalyst supporting area 75 mm × 75 mm, titanium oxide supporting amount about 0.1 g) was placed in a glass container having a volume of 20 L (liter), and the inside of the container was replaced with artificial air. After that, acetaldehyde gas was injected into the container so as to have a concentration of 20 ppm. Next, the titanium oxide photocatalyst was irradiated with a germicidal lamp having a wavelength of 254 nm, and the acetaldehyde concentration in the container was 1 ppm.
The time required to reach the following was measured with a gas monitor. The surface of the produced titanium oxide photocatalyst was observed by SEM.
Went by. The artificial air (manufactured by Nippon Oxygen Co., Ltd.) used had a gas composition of nitrogen 78%, oxygen 21%, and argon 0.9.
%, Carbon dioxide (CO, CO 2 , CH 4 ) 0.03%, the balance being water.
【００８０】表２に各実施例および比較例における特性
評価結果を示す。Table 2 shows the results of characteristic evaluation in each of the examples and comparative examples.
【００８１】[0081]
【表２】 [Table 2]
【００８２】表２の結果から以下のことがわかる。柱状
中空構造の酸化チタン結晶光触媒材料であって、Ｐｔ微
粒子担持処理を施していない比較例１は、高さ３０００
〜５０００ｎｍ、巾３００〜５００ｎｍの柱状中空結晶
である光触媒結晶体からなる集合体を形成していること
が、ＳＥＭ観察により確認された。アセトアルデヒドの
分解時間は１５ｍｉｎであり、後述する比較例２と比較
して約２分の１にまで分解所要時間が短縮され、分解効
率は約２倍にまで向上し、本発明の貴金属微粒子担持技
術を適用しない段階のものであっても、既に従来技術よ
りも充分に分解性能が高く、高活性の光触媒機能を有す
るものであることが示された。The following can be seen from the results in Table 2. A comparative example 1 which is a titanium oxide crystal photocatalyst material having a columnar hollow structure and not subjected to the Pt fine particle supporting treatment has a height of 3000.
It was confirmed by SEM observation that an aggregate consisting of photocatalyst crystal bodies, which are columnar hollow crystals with a width of up to 5000 nm and a width of 300 to 500 nm, was formed. The decomposition time of acetaldehyde is 15 min, the time required for decomposition is shortened to about half as compared with Comparative Example 2 described later, the decomposition efficiency is improved to about twice, and the noble metal fine particle supporting technology of the present invention is achieved. It has already been shown that even in the stage of not applying, the photocatalytic function has a sufficiently high decomposition performance and a high activity as compared with the prior art.
【００８３】粉末状の光触媒材料である比較例２は、粒
径２０〜３０ｎｍの酸化チタン粒子が多数存在している
ことがＳＥＭ観察により確認された。アセトアルデヒド
の分解時間は２８ｍｉｎだった。It was confirmed by SEM observation that Comparative Example 2, which is a powdery photocatalytic material, contains a large number of titanium oxide particles having a particle size of 20 to 30 nm. The decomposition time of acetaldehyde was 28 min.
【００８４】上記比較例１および２に対し、実施例１〜
３は、柱状中空構造を有する酸化チタン結晶光触媒材料
であって、上述の貴金属担持処理を施すことにより、柱
状中空構造の酸化チタン結晶光触媒の表面に粒径１〜５
０ｎｍのＰｔ微粒子を担持させたものである。以下に各
実施例の結果を示す。In contrast to Comparative Examples 1 and 2 above, Examples 1 to 1
No. 3 is a titanium oxide crystal photocatalyst material having a columnar hollow structure, and the titanium oxide crystal photocatalyst having a columnar hollow structure has a particle size of 1 to 5 when subjected to the above-mentioned noble metal supporting treatment.
The Pt fine particles of 0 nm are supported. The results of each example are shown below.
【００８５】実施例1は、湿式法により柱状中空構造の
酸化チタン光触媒にＰｔ微粒子を担持させた光触媒材料
である。得られた光触媒材料は、柱状中空構造の酸化チ
タン結晶表面に粒径１〜５０ｎｍ程度のＰｔ微粒子が担
持されていると予想される。Example 1 is a photocatalyst material in which Pt fine particles are supported on a titanium oxide photocatalyst having a columnar hollow structure by a wet method. It is expected that the obtained photocatalyst material has Pt particles having a particle size of about 1 to 50 nm supported on the surface of the titanium oxide crystal having a columnar hollow structure.
【００８６】所定容積空間内における濃度２０ｐｐｍの
アセトアルデヒドガスを１ｐｐｍ以下に低減するのに要
する時間、すなわちアセトアルデヒドの分解時間は８ｍ
ｉｎであり、比較例２の２８ｍｉｎと比較して分解時間
は３分の１以下にまで短縮することができ、分解効率は
３倍以上にまで向上し、従来技術の特性を極めて大きく
改良することができた。また、比較例１の１５ｍｉｎと
比較しても分解時間は約２分の１にまで短縮することが
でき、分解効率は約２倍にまで向上し、先になされた本
願発明者らによる柱状中空構造の酸化チタン光触媒材料
の特性をも大幅に改良することができ、非常に分解性能
が高く、高活性の光触媒機能を有する光触媒材料である
ことが示された。The time required to reduce the acetaldehyde gas having a concentration of 20 ppm in the predetermined volume space to 1 ppm or less, that is, the decomposition time of acetaldehyde is 8 m.
In, the decomposition time can be shortened to less than one-third as compared with 28 min of Comparative Example 2, the decomposition efficiency can be improved to more than three times, and the characteristics of the prior art can be greatly improved. I was able to. In addition, the decomposition time can be shortened to about one half even when compared with 15 min of Comparative Example 1, and the decomposition efficiency is improved to about twice, and the columnar hollow by the inventors of the present invention that was previously made It was shown that the characteristics of the titanium oxide photocatalyst material having the structure can be greatly improved, that the photocatalyst material has a very high decomposition performance and a highly active photocatalytic function.
【００８７】実施例２は、還元処理を含む湿式法により
柱状中空構造の酸化チタン光触媒にＰｔ微粒子を担持さ
せた光触媒材料である。得られた光触媒材料は、柱状中
空構造の酸化チタン結晶表面に粒径１〜５０ｎｍ程度の
Ｐｔ微粒子が担持されていると予想される。Example 2 is a photocatalyst material in which Pt fine particles are supported on a titanium oxide photocatalyst having a columnar hollow structure by a wet method including a reduction treatment. It is expected that the obtained photocatalyst material has Pt particles having a particle size of about 1 to 50 nm supported on the surface of the titanium oxide crystal having a columnar hollow structure.
【００８８】所定容積空間内における濃度２０ｐｐｍの
アセトアルデヒドガスを１ｐｐｍ以下に低減するのに要
する時間、すなわちアセトアルデヒドの分解時間は６ｍ
ｉｎであり、比較例２の２８ｍｉｎと比較して分解時間
は４分の１〜５分の１程度にまで短縮することができ、
分解効率は約４〜５倍程度にまで向上し、従来技術の特
性を極めて大きく改良することができた。また、比較例
１の１５ｍｉｎと比較しても分解時間は５分の２にまで
短縮することができ、分解効率は２．５倍にまで向上
し、先になされた本願発明者らによる柱状中空構造の酸
化チタン光触媒材料の特性をも大幅に改良することがで
き、非常に分解性能が高く、高活性の光触媒機能を有す
る光触媒材料であることが示された。The time required to reduce the acetaldehyde gas having a concentration of 20 ppm in the predetermined volume space to 1 ppm or less, that is, the decomposition time of acetaldehyde is 6 m.
In, the decomposition time can be shortened to about 1/4 to 1/5 as compared with 28 min of Comparative Example 2,
The decomposition efficiency was improved to about 4 to 5 times, and the characteristics of the prior art could be greatly improved. In addition, the decomposition time can be shortened to 2/5 even when compared with 15 min of Comparative Example 1, the decomposition efficiency is improved to 2.5 times, and the above-mentioned columnar hollow by the present inventors It was shown that the characteristics of the titanium oxide photocatalyst material having the structure can be greatly improved, that the photocatalyst material has a very high decomposition performance and a highly active photocatalytic function.
【００８９】また、実施例２の特性は実施例１の分解性
能をも凌ぐものであり、貴金属微粒子担持処理では酸化
チタン光触媒表面に担持された貴金属の還元処理によ
り、光触媒機能が一層高感度のものとなることが示され
た。Further, the characteristics of Example 2 exceed the decomposition performance of Example 1, and in the noble metal fine particle supporting treatment, the reduction treatment of the noble metal supported on the titanium oxide photocatalyst surface makes the photocatalytic function more sensitive. It was shown to be a thing.
【００９０】実施例３は、ＰＶＤ法の一つであるスパッ
タ法により柱状中空構造の酸化チタン光触媒にＰｔ微粒
子を担持させた光触媒材料である。得られた光触媒材料
は、柱状中空構造の酸化チタン結晶表面に粒径１〜５０
ｎｍ程度のＰｔ微粒子が担持されていると予想される。Example 3 is a photocatalyst material in which Pt fine particles are supported on a titanium oxide photocatalyst having a columnar hollow structure by a sputtering method which is one of PVD methods. The obtained photocatalytic material has a particle size of 1 to 50 on the surface of the titanium oxide crystal having a columnar hollow structure.
It is expected that Pt fine particles of about nm are supported.
【００９１】所定容積空間内における濃度２０ｐｐｍの
アセトアルデヒドガスを１ｐｐｍ以下に低減するのに要
する時間、すなわちアセトアルデヒドの分解時間は６ｍ
ｉｎであり、比較例２の２８ｍｉｎと比較して分解時間
は４分の１〜５分の１程度にまで短縮することができ、
分解効率は約４〜５倍程度にまで向上し、従来技術の特
性を極めて大きく改良することができた。また、比較例
１の１５ｍｉｎと比較しても分解時間は５分の２にまで
短縮することができ、分解効率は２．５倍にまで向上
し、先になされた本願発明者らによる柱状中空構造の酸
化チタン光触媒材料の特性をも大幅に改良することがで
き、非常に分解性能が高く、高活性の光触媒機能を有す
る光触媒材料であることが示された。The time required to reduce the acetaldehyde gas having a concentration of 20 ppm in the predetermined volume space to 1 ppm or less, that is, the decomposition time of acetaldehyde is 6 m.
In, the decomposition time can be shortened to about 1/4 to 1/5 as compared with 28 min of Comparative Example 2,
The decomposition efficiency was improved to about 4 to 5 times, and the characteristics of the prior art could be greatly improved. In addition, the decomposition time can be shortened to 2/5 even when compared with 15 min of Comparative Example 1, the decomposition efficiency is improved to 2.5 times, and the above-mentioned columnar hollow by the present inventors It was shown that the characteristics of the titanium oxide photocatalyst material having the structure can be greatly improved, that the photocatalyst material has a very high decomposition performance and a highly active photocatalytic function.
【００９２】実施例１〜３ではＰｔを担持貴金属とした
が、その他、Ｐｄ、Ａｕ、Ｉｒ、Ｒｈ、Ｒｕを光触媒の
表面に担持させても、光触媒機能の高活性化を達成する
ことができる。このことは実験により確認済みである。In Examples 1 to 3, Pt was used as the supported noble metal. However, even if Pd, Au, Ir, Rh, and Ru are supported on the surface of the photocatalyst, high activation of the photocatalytic function can be achieved. . This has been confirmed by experiments.
【００９３】なお、特性評価はアセトアルデヒドだけで
はなく、トルエン、キシレン、スチレン、トリメチルア
ミン等他の有機化合物でも行い、本発明の貴金属担持の
光触媒材料はこれらにおいてもアセトアルデヒドの場合
と同様の分解性能、高活性の光触媒機能を有することが
確認された。The characteristic evaluation was carried out not only with acetaldehyde but also with other organic compounds such as toluene, xylene, styrene and trimethylamine. The noble metal-supported photocatalyst material of the present invention has the same decomposition performance and high performance as those of acetaldehyde. It was confirmed to have an active photocatalytic function.
【００９４】[0094]
【発明の効果】本発明に係る光触媒材料によれば、以上
のように構成されているため、極めて高活性の光触媒機
能を達成することができる。また、光触媒材料の飛散や
脱落がなくて取り扱いが容易であり、環境浄化装置等に
も組み込みやすく、製造コストを低減することができ
る。Since the photocatalyst material according to the present invention is configured as described above, it is possible to achieve an extremely high activity photocatalytic function. In addition, the photocatalyst material does not scatter or fall off, is easy to handle, and can be easily incorporated into an environmental purification device or the like, and the manufacturing cost can be reduced.
【００９５】さらに本発明に係る光触媒材料は、極めて
高活性の光触媒機能により、清浄機能、抗菌機能、脱臭
機能、防汚機能等において顕著な効果を有し、空気清浄
機、脱臭機、冷暖房機等の各種空調機器あるいは清水器
や水質浄化機器などの環境浄化装置に、広く応用するこ
とができる。Further, the photocatalyst material according to the present invention has a remarkable effect in cleaning function, antibacterial function, deodorizing function, antifouling function, etc. due to the extremely high activity of the photocatalytic function, and has an air purifier, a deodorizer, an air conditioner. It can be widely applied to various air conditioners such as the above, or environmental purification devices such as water purifiers and water purification devices.
【図１】本発明の光触媒材料の外観を示す模式図であ
る。FIG. 1 is a schematic view showing the appearance of a photocatalyst material of the present invention.
【図２】本発明の光触媒材料製造方法の一つについて、
その構成を示すフロー図である。FIG. 2 shows one of the methods for producing a photocatalyst material of the present invention,
It is a flowchart which shows the structure.
【図３】本発明の他の光触媒材料製造方法について、そ
の構成を示すフロー図である。FIG. 3 is a flowchart showing the structure of another method for producing a photocatalyst material according to the present invention.
【図４】図２および図３における原光触媒材料作製工程
Ｐ１の構成を示すフロー図である。FIG. 4 is a flow diagram showing a configuration of a raw photocatalyst material manufacturing step P1 in FIGS. 2 and 3.
【図５】Ｐｔを担持する例について、その工程を示した
フロー図である。FIG. 5 is a flow chart showing the steps of an example of supporting Pt.
【図６】既開発の柱状中空構造を有する酸化チタン結晶
による光触媒材料の外観を示す模式図である。FIG. 6 is a schematic view showing the appearance of a photocatalyst material made of titanium oxide crystals having a columnar hollow structure that has already been developed.
１、５１…光触媒材料担持体、 ２、５２…基部（結晶
核）、 ３、５３…光触媒結晶体（柱状構造の酸化チタ
ン結晶)、 ５…貴金属微粒子、 １０、６０…光触媒
材料、 ２０、７０…光触媒体、 Ｐ１…原光触媒材料
作製工程、 Ｐ２…貴金属担持工程、 Ｐ３…貴金属担
持工程（ＰＶＤ工程）、 Ｐ２１…吸着工程、 Ｐ２２
…乾燥熱処理工程、 Ｐ２３…還元工程、 ３１…ゲル
化工程、３２…固化工程、 ３３…熱処理工程、 Ｓ１
…結晶核、 Ｓ２…ゾル溶液、Ｍ３…光触媒材料の原
型、 Ｍ４…固化した原型、Ｍ５…原光触媒材料1, 51 ... Photocatalyst material supporting body, 2, 52 ... Base (crystal nucleus), 3, 53 ... Photocatalyst crystal body (columnar structure titanium oxide crystal), 5 ... Noble metal fine particles, 10, 60 ... Photocatalyst material, 20, 70 ... Photocatalyst body, P1 ... Original photocatalyst material preparation step, P2 ... Noble metal supporting step, P3 ... Noble metal supporting step (PVD step), P21 ... Adsorption step, P22
... Drying heat treatment step, P23 ... Reduction step, 31 ... Gelation step, 32 ... Solidification step, 33 ... Heat treatment step, S1
... Crystal nuclei, S2 ... Sol solution, M3 ... Prototype of photocatalytic material, M4 ... Solid prototype, M5 ... Original photocatalytic material
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 37/18 Ｂ０１Ｊ 37/18 // Ａ６１Ｌ 9/00 Ａ６１Ｌ 9/00 Ｃ (72)発明者 長谷川 章 青森県八戸市田面木字上野平16番１号 八 戸工業高等専門学校内 (72)発明者 壬生 隆史 青森県八戸市大字根城字丹後平33−15 (72)発明者 工藤 武志 青森県八戸市大字市川町字長七谷地２番 672号 アンデス電気株式会社内 (72)発明者 中村 友宇子 青森県八戸市大字市川町字長七谷地２番 672号 アンデス電気株式会社内 (72)発明者 類家 東 青森県八戸市大字市川町字長七谷地２番 672号 アンデス電気株式会社内 Ｆターム(参考） 4C080 AA07 BB04 BB05 CC02 CC09 HH05 JJ01 KK08 LL03 MM02 NN01 QQ03 4G069 AA03 AA08 BA04A BA04B BA48A BB08C BB20C BC32A BC33A BC69A BC75A BC75B BD12C CA17 CD10 DA05 EA06 EB01 EC27 EC28 FA01 FA02 FA03 FB02 FB08 FB14 FB23 FB30 FB44 FB80 FC02─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B01J 37/18 B01J 37/18 // A61L 9/00 A61L 9/00 C (72) Inventor Akira Hasegawa Aomori No. 16-1 Uenohira, Tamenoki, Hachinohe-shi, Japan (72) Inside the Hachinohe National College of Technology (72) Inventor Takashi Mibu 33-15, Tangodai, Negoji, Hachinohe, Aomori Prefecture (72) Takeshi Kudo Hachinohe, Aomori-shi, Aomori Prefecture Kawamachi-cho Nagachitanachi No. 2 672 Andes Electric Co., Ltd. (72) Inventor Yuuko Nakamura No. 2 672 Nagachichichi, Nagachiyachi, Ichikawacho, Hachinohe-shi, Aomori Prefecture Andes Electric Co., Ltd. No. 2 672 Nagachitanachi, Ichikawa-cho, Hachinohe-shi, Aomori F-Term (Reference) within Andes Electric Co., Ltd. (reference) 4C080 AA07 BB04 BB05 CC02 CC09 HH05 JJ01 KK08 LL03 MM02 NN01 QQ03 4G069 AA03 AA0 8 BA04A BA04B BA48A BB08C BB20C BC32A BC33A BC69A BC75A BC75B BD12C CA17 CD10 DA05 EA06 EB01 EC27 EC28 FA01 FA02 FA03 FB02 FB08 FB14 FB23 FB30 FB44 FB80 FC02
Claims (10)
めの基部、または光触媒材料担持体の表面に固定されて
いる基部と、該基部から伸長する柱状の光触媒結晶体
と、からなる光触媒材料であって、該光触媒材料の表面
には貴金属微粒子が担持されていることを特徴とする、
光触媒材料。1. A photocatalyst material comprising a base portion fixed to the surface of a photocatalyst material carrier, or a base portion fixed to the surface of the photocatalyst material carrier, and a columnar photocatalyst crystal body extending from the base portion. And characterized in that noble metal fine particles are carried on the surface of the photocatalytic material,
Photocatalytic material.
めの基部、または光触媒材料担持体の表面に固定されて
いる基部と、該基部から伸長する中空の柱状構造をとる
光触媒結晶体と、からなる光触媒材料であって、該光触
媒材料の表面には貴金属微粒子が担持されていることを
特徴とする、光触媒材料。2. A base to be fixed on the surface of the photocatalyst material carrier, or a base fixed to the surface of the photocatalyst material carrier, and a photocatalyst crystal body having a hollow columnar structure extending from the base. A photocatalyst material comprising: a photocatalyst material, characterized in that noble metal fine particles are carried on the surface of the photocatalyst material.
なる構造が存在していることを特徴とする、請求項２に
記載の光触媒材料。3. The photocatalyst material according to claim 2, wherein a structure composed of photocatalyst particles is present inside the photocatalyst crystal body.
触媒材料であって、触媒担持面積が７５ｍｍ×７５ｍｍ
の光触媒材料担持体上に担持された担持量約０．１ｇの
光触媒を用いてなる該光触媒材料を用いてアセトアルデ
ヒドガスを分解させた場合に、容積２０リットルのガラ
ス製容器中のアセトアルデヒドガス濃度を２０ｐｐｍか
ら１ｐｐｍ以下にするための所要時間が５分以上１０分
間以下であることを特徴とする、光触媒材料。4. The photocatalyst material according to claim 1, wherein the catalyst supporting area is 75 mm × 75 mm.
When the acetaldehyde gas is decomposed by using the photocatalyst material having a carrying amount of about 0.1 g carried on the photocatalyst material carrier, the acetaldehyde gas concentration in a glass container having a volume of 20 liters is A photocatalyst material, characterized in that the time required for reducing from 20 ppm to 1 ppm is 5 minutes or more and 10 minutes or less.
部が結晶核であり、前記貴金属は白金であることを特徴
とする、請求項１ないし４のいずれかに記載の光触媒材
料。5. The photocatalyst material according to claim 1, wherein the photocatalyst is titanium oxide, the base is a crystal nucleus, and the noble metal is platinum.
体上に担持された請求項１ないし５のいずれかに記載の
光触媒材料と、からなる光触媒体。6. A photocatalyst body comprising a photocatalyst material carrier and the photocatalyst material according to claim 1 carried on the photocatalyst material carrier.
材料を得る原光触媒材料作製工程と、得られた原光触媒
材料の表面に貴金属微粒子を担持するための貴金属担持
工程とからなる光触媒材料製造方法であって、該貴金属
担持工程は、光触媒材料を貴金属化合物溶液に浸漬して
貴金属粒子を光触媒材料表面に吸着、担持する吸着工程
と、貴金属が吸着、担持された光触媒材料を乾燥し次い
で熱処理する乾燥熱処理工程と、を含むことを特徴とす
る、光触媒材料製造方法。7. A method for producing a photocatalyst material comprising a raw photocatalyst material producing step for obtaining a photocatalyst material on which noble metal is not supported on a surface, and a precious metal supporting step for supporting noble metal fine particles on the surface of the obtained raw photocatalyst material. In the step of supporting the noble metal, the photocatalyst material is immersed in a solution of the noble metal compound to adsorb and carry the noble metal particles on the surface of the photocatalyst material, and the photocatalyst material on which the noble metal is adsorbed and carried is dried and then heat-treated. A dry heat treatment step, and a method for producing a photocatalytic material.
材料表面に担持された酸化状態の貴金属微粒子を還元す
るための還元工程を設けることを特徴とする、請求項７
に記載の光触媒材料製造方法。8. The reducing step for reducing the oxidized noble metal fine particles carried on the surface of the photocatalytic material is provided after the dry heat treatment step.
The method for producing a photocatalyst material according to 1.
（VI）酸六水和物等の白金を含む化合物であることを特
徴とする、請求項７または８に記載の光触媒材料製造方
法。9. The method for producing a photocatalyst material according to claim 7, wherein the noble metal compound is a compound containing platinum such as hexachloroplatinum (VI) acid hexahydrate.
媒材料を得る原光触媒材料作製工程と、得られた原光触
媒材料の表面に貴金属を担持するため貴金属担持工程と
からなる光触媒材料製造方法であって、該貴金属担持工
程は、スパッタリング法、真空蒸着法、またはその他の
物理的蒸着法により原光触媒材料の表面に貴金属微粒子
を担持させる工程であることを特徴とする、光触媒材料
製造方法。10. A method for producing a photocatalyst material, which comprises a raw photocatalyst material producing step for obtaining a photocatalyst material in which no precious metal is not supported on the surface, and a precious metal carrying step for carrying a precious metal on the surface of the obtained raw photocatalyst material. The photocatalytic material manufacturing method is characterized in that the noble metal supporting step is a step of supporting the noble metal fine particles on the surface of the raw photocatalytic material by a sputtering method, a vacuum vapor deposition method, or another physical vapor deposition method.
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